: = eee Mia CSU RV Ey OF THE MeeANIC COLOURING MATTERS pee EAC SURVEY OF THE ORGANIC COLOURING MATTERS BY Meewe SCHULTZ ann P. JULIUS TRANSLATED AND EDITED, WITH EXTENSIVE ADDITIONS BY Pereenil ho GG. GRE PINS TiC ib Ons: INER IN COAL-TAR PRODUCTS TO THE CITY AND GUILDS OF LONDON INSTITUTE EXAM ae oY ; bY OOO , \ Ye HInlA ' atone a yn eal P ’ Lonvoit MA CM TIAAANe ANG IDAEGe Gn AND NEW YORK 1894 All rights reserved EDITOR'S PREFACE THE publication of an English Edition of Drs. Schultz and Julius’ valuable tables of the coal- tar colours will, it is hoped, supply a want which has long been felt in this country. The rapid progress of the coal-tar colour industry and the continual increase in number and complexity of the products employed in the tinctorial arts, render a knowledge of the chemistry and technology of these products of increasing importance. It is consequently hoped that this work will be found valuable not only to the technical Chemist, but also to the Dyer, Analyst, ~ Merchant, Patent-Agent, etc., and in fact to every one concerned with the production, handling, or use of the coal-tar colours. The Editor has brought the tables up to date by the insertion of about fifty new colours which have made their appearance since the publication of the German edition, and has rendered the work more serviceable to English readers by giving references to British and American Patents whenever these exist. In view of the want of any complete technological handbook on Coal-tar Chemistry in the English language, the Editor has felt that it would render the work more complete and greatly increase its utility to add at the commencement a short but complete account of those organic compounds which are employed as primary or intermediary products for the preparation of the colouring matters, and which necessarily find no mention in the tables themselves. This the Editor has endeavoured to give in as concise a form as possible, so as to carry out the fundamental idea of the Authors, but at the same time to render the description as full in essential details and as consistent as possible with the most recent knowledge. Accordingly only those methods of preparation are described which, so far as is known, are practically employed, no mention being made of merely laboratory methods, for which the ordinary text-books may be consulted, nor of processes which, though formerly in use, have now been abandoned. In the same way only those references have been given which are technically of most importance. The proportions and methods of ee) procedure have been described with as much detail as space allowed, especially with regard to the most important compounds. Tables for the identification and analysis of the various colouring matters have also been added. It is trusted that the whole will form a concise and complete compendium of the technology of the subject, in a form convenient for reference. Owing to the exigencies of the English language, and to the desirability of uniformity, it has been found necessary to modify the nomenclature employed by the Authors for the azo- colours, and to bring it into accord with that usually employed in this country. The Editor desires to express his thanks to the following Firms, to whom he is indebted for much valuable information relating to new colours :— THE BADISCHE ANILIN- und SODAFABRIK. BROOKE, SIMPSON & SPILLER, LIMITED. L. CASSELLA & Co., FRANKFURT. THE CLAYTON ANILINE Co., LIMITED, MANCHESTER. Daun & Co., BARMEN. L. DuRAND, HUGUENIN & Co., BASLE. J. R. Geicy & Co., BASLE. A. LEONHARDT & Co., MUHLHEIM. K, OEHLER, OFFENBACH. LA SocrETé POUR L-INDUSTRIE CHIMIQUE A BALE. Lonpon, April 1894, ABBREVIATIONS NAMES oF FIRMS pA. | Actiengesellschaft fiir Anilinfabrikation, Berlin. (B.| Badische Anilin- und Sodafabrik, Ludwigshafen a./Rhein. [B. K.] Leipziger Anilinfabrik Beyer & Kegel, Lindenau-Leipzig. [B. S. S.] Brooke, Simpson & Spiller, Limited, Atlas Works, Hackney Wick, London, E. [ By. | Farbenfabriken vorm. Fr. Bayer & Co., Elberfeld. [C.] Leopold Cassella & Co., Frankfurt a./M. [C7. Co.] The Clayton Aniline Co., Limited, Clayton, near Manchester. [ Cz. ] Casthelaz & Bruére, Rouen. [D.] Dahl & Co., Barmen. [D. H.| 1. Durand, Huguenin & Co., Basle, St. Fons & Hiiningen. [G.] J.B. Geigy, Basle. [G. M.| Guinon, Marnas & Bonnet, now Guinon, Picard & Jay, St. Fons. [| H.] Read Holliday & Sons, Limited, Huddersfield. [H. R.| Henriet, Roman & Vignon, of Lyon-Vaise, and the Manufacture Lyonnaise des Matieres Colorantes. [L.] Société pour l’Industrie Chimique (formerly Bindschedler & Busch), Basle. [K.] Kalle & Co., Biebrich a./Rhein. [K. S.] Kern & Sandoz, Basle. [Z. ] A. Leonhardt & Co., Miihlheim, near Frankfurt. PEED. | Leverkus & Sohne, Leverkusen. [M.] Farbwerke vorm. Meister, Lucius & Briining, Hochst a./Main. [Mo. | Gilliard, Monnet & Cartier, Lyons. [NV.] C. Neuhaus, Elberfeld. [0.] K. Oehler, Offenbach a./Main. val Société Anonyme des Matieres Colorantes de St. Dennis, Paris. [ Sch. | The Schéllkopf Aniline and Chemical Co., Buffalo, U.S.A. [7. M.| Tillmanns, Ter Mer & Co., Uerdingen. [W. N.| Farbwerke Griesheim, W. Notzel, Griesheim. Am. Pat. Ann. Ann. Chim. Phys. Ber. Bl. Bull. de Mulhouse Chem. Ind. Chem. News Chem. Ztg. C. R. Ding. pol. J. Eng. Pat. Fr. Pat. Farbztg. Ger. Pat. Jahresber. J. Chem. Soe. J. Soe. Chem. Ind. J. Soe. Dyers. Jour. pr. Chem. Mon. f. Chem. Mon. Scien. Pogg. Ann. Proe. Chem. Soc. Wagner’s Jahresber. Zeits. f. Chem. [ Syaiee VEFERENCES United States Patent. Liebig’s Annalen der Chemie. Annales de Chimie et de Physique. Berichte der Deutschen chemischen Gesellschaft. Bulletin de la Société Chimique. Bulletin de la Société Industrielle de Mulhouse. Die Chemische Industrie. Chemical News. Chemiker Zeitung. Comptes rendus hebdomadaires des séances de l’académie des sciences. Dingler’s polytechnisches Journal. English Patent. French Patent. Lehne’s Farber Zeitung. German Patent. Jahresbericht tiber die Fortschritte der Chemie. Journal of the Chemical Society. Journal of the Society of Chemical Industry. Journal of the Society of Dyers and Colorists. Journal fiir praktische Chemie. Monatshefte fiir Chemie. Le Moniteur Scientifique. Poggendorf’s Annalen der Physik und Chemie. Proceedings of the-Chemical Society. Jahresbericht iiber die Leistungen der Chemischen Technologie. Zeitschrift fiir Chemie. Neue Folge. RAW PRODUCTS COAL TAR CoAL Tar, the primary raw material of the colour industry, is obtained in the manufacture of coal gas, accumulating in the hydraulic mains, condensers, and scrubbers of the gas works. Of recent years, however, a large and constantly increasing quantity has been obtained from the coke-ovens used for making hard coke for metallurgical purposes. In the latter case the gas evolved, instead of being used at once for heating the ovens, is first passed through a system of condensers and scrubbers, by means of which the tar and ammonia are removed and collected. In addition to coal tar, another source of aromatic compounds, though at present only employed to a very limited extent, is furnished by the residues of the petroleum industry, which, when submitted to a high temperature, yield a tar rich in aromatic hydro- carbons, but containing very little phenols (¢f Ger. Pat. 51553). The average quantity of gas tar worked up per annum is given at 350,000 tons for England and 530,000 tons for the whole world, whilst the quantity of coke-oven tar, though constantly increasing, probably does not at present exceed 50,000 tons. It may be expected, however, that with the more general introduction of electricity for lighting purposes and the consequent diminution of the supply of gas tar, the coke-oven tar will eventually become the main source of our aromatic hydro- carbons, it being estimated that the coke-ovens now in work, if all fitted with condensing arrangements, would be capable of supplying the whole of the tar at present required. More- over, only about 107 of the total benzene formed in the distillation of coal is contained in the tar; the remaining 90'/ which occurs in the gas is at present lost for the purposes of the colour industry, but might be readily extracted if the gas were only employed as a heating agent. Coal tar, a black viscid liquid of sp. gr. 1-1 to 1-2, is a very complex mixture, con- taining, together with finely divided carbon, a great number of bodies (hydrocarbons, phenols, bases, etc.), of which the following are the most important. I. Hydrocarbons Formula. Melting Point. Boiling Point. Crotonylene . ‘ : : : CsH, Fluid 20° Hydrocarbons of the ethylene series CrHon — we Hydrocarbons of the methane series CnHon +s ee sie Benzene . é ; é : : C.H, 3 81° Toluene . : : : C,H, Fluid nba labs o-Xylene . ; ; : : F CyHi9 a 142° m-Xylene ; : : ' CsHyy i 139° p-Xylene . : : ; 3 5 CyHio aL BR Styrene . : : : . : C3H, Fluid 146° Mesitylene . ; : : 4 Cy Hie 4, 163° Pseudocumene 3 : : : C,H,» i ; 166° Naphthalene . , , : . CyoHg 80° 218° Methylnaphthalene ; : ; Cy io a Fluid ; B 33° 242° Dipheny] . : : ; : : Cy2Hj0 rally 254° Acenaphthene . : : ; ; Cy2H,y 99° 280° Fluorene ; é: : ; Cy3Hi0 113° 295° Phenanthrene . : : C,4Hi0 100° 340° Fluoranthrene b ; : ; C,H 109° Above 360° Anthracene. ; : : : C,H IVS" ws Methylanthracene . : : : C,; Hy» 200° 3 Pyrene . “ ‘ ‘ 5 2 CigHio 149° a5 Chrysene. : F : : : C,.Hie 250° + Picene or Parachrysene . : : Ci. 4 239° 520° soul — bo pe Il. Other Neutral Bodies Formula, Melting Point. Boiling Point. Carbon disulphide . : ; CS» Fluid 47° Ethyl alcohol . , : 4 ‘ 'C.H;. OH = 78° Acetonitrile . : ; : ; CoH3N 5 82° Thiophene. : : : ; CyH.S Fe 84° Thiotolene . é : i : CsH.S Ae isis Thioxene , ; : : CeH3S . Tote Benzonitrile . ; , C,H;N % 191° Phenythiocarbimide : 4 : C,H;NS es 220° Carbazole : : Cy2H oN 238° 355. Phenylnaphthylearbazole : : CigHuiN 330° Above 440° Coumarone . : : CsH,gO Fluid yar Ill. Bases Formula, Melting Point. Boiling Point. Pyridine : . : : ; CsHsN Fluid ish Pyrrol . ; ‘ ‘ ; F CsH;N a 126° Picoline . : 5 ; : 5 CesH,N 9 134° Lutidine : : ; ; : C7HoN a 154° recone ‘ ; : : 3 Cou a ‘a 2 Nniline . Fi : . . Fi 6f17. aa Quinoline ; : ¢ : ; CoH,;N if 239° Quinaldine . ; " , 2 CipoH oN Pa 243° Acridine : : g : 5 CigHoN 107° Above 360° IV. Phenols Formula. Melting Point. Boiling Point, Phenol . ; ; ; , CsH.O 42° : 188° o-Cresol . : ‘ : ; ; C,;Hg0 3 ke 188° p-Cresol . ; ; : ; C,H,O0 36° 198° m-Cresol : ; C7HsO Fluid 201° a- Naphthol ; ’ ‘ : ‘ CyoHgO 94° 280° 6-Naphthol . Ci9HgO 123m 286° Xylenols and other high boiling su Bic sa phenols The proportions of these constituents vary greatly with the kind of coal employed and with the temperature to which the gas retorts are heated. Usually the aromatic hydrocarbons greatly predominate, and only small quantities of the hydrocarbons of the methane and ethylene series are present, but by employment of cannel coal or a low temperature in the retorts, the quantity of the fatty hydrocarbons is much increased, and the value of the tar consequently diminished. The proportion of thiophene and its homologues depends upon the quantity of sulphur in the coal, Scotch and German tar usually containing much more than English. Of the many constituents of coal tar the only ones which are at present employed in the colour industry are benzene, toluene, xylene, naphthalene, anthracene, phenol, and cresol. Gas tar contains about 1°/ of benzene, 8 to 10% of naphthalene, and }'/ of anthracene. Coke-oven tar contains about 1°/ of benzene, 4 to 5% of naphthalene, and 2°/ of anthracene. In order to isolate the valuable products, the tar is first submitted to a preliminary distillation from large wrought-iron stills, capable of holding from 10 to 40 tons, by which it is separated into the following portions :— [so A. First runningss : up to 110°} ‘ B lightolls . . . . 110°togior jf ° te 8% of the tar C. Carbolic oils. Mee to 2408 Biol rs D. Heavy or creosote oils. . 240° to 270° Stee LO as EK. Anthracene oils : 2 270 to 400° 16°to 207, 55 whilst a residue of pitch remains behind in the still (about 50°/). From the “ first runnings ” and “light oils” the benzene, toluene, and xylene are obtained: from the “ carbolic oils” the phenol, cresol, and naphthalene ; and from the “anthracene oils” anthracene. In the further working up of the “ first runnings” and “light oils” these products are first submitted to a fractional distillation, by means of which a low boiling portion (containing acetonitrile, fatty hydrocarbons, and carbon disulphide) and a high boiling portion (returned to the “ carbolic ” or “creosote oils”) are removed. The middle portion is then subjected to a series of washings with caustic soda, strong sulphuric acid, and finally water; the caustic soda removes phenols and the sulphuric acid removes bases (pyridine, quinoline, etc.), phenols, hydrocarbons of the acetylene and ethylene series, naphthalene, and thiophene compounds. The product is again submitted to fractional distillation, and from the “crude benzol” thus obtained pure benzene, toluene, and xylene are separated by rectification in a “Savalle” still. The latter is a still of peculiar construction, in which the vapour is caused to pass through a long column divided into a series of chambers by perforated plates, in which the higher boiling portions are con- densed and returned to the still. The hydrocarbons distilling after the xylene (e.g. cumene, etc.) have at present found no use in the colour industry, but are usually employed as “solvent naphtha.” The “crude benzol” from Scotch and German tars contains considerable quantities (often 17/) of thiophene and its homologues, which must be removed, previously to the final rectification in the Savalle still, by agitation with 57 of conc. sulphuric acid; this is not always necessary with benzol from English tar. Naphthalene is obtained from the “carbolic” and “heavy oils,’ from which large quantities crystallise out on standing, and is separated by centrifugating and pressing. Further quantities are also obtained from the “carbolic oils” after the phenols have been removed by treatment with caustic soda, and from the so-called “dead oils” obtained in the rectification of the “ first runnings” and “light oils.” The crude naphthalene is washed with hot aqueous caustic soda to remove phenols, and then agitated with 5 to 10% of cone. sulphuric acid to remove bases, residual phenols, and other impurities, after which it is washed with very dilute alkali and finally distilled or sublimed. The naphthalene thus obtained is nearly chemically pure, and is used for the manufacture of naphthols, naphthylamines, phthalic acid, etc. For the extraction of phenol and cresol the “carbolic oils” are agitated with a dilute solution of caustic soda, sufficient to dissolve the phenols. The aqueous alkaline liquor is drawn off from the oil, and steam is blown through it to remove small quantities of naphthalene and other hydrocarbons which it still contains. The phenols are then pre- eipitated by neutralisation with sulphuric, hydrochloric, or carbonic acid, separated from the liquor and submitted to a series of fractional distillations. The phenol is thus obtained chemically pure as a white solid, melting at 42°, the cresol as a fluid mixture of the three isomers. The higher phenols are not isolated, but are used for the “creosoting” of timber. Phenol and cresol, as also the salicylic and cresotinic acid, made from them, are largely em- ployed as antiseptic and medicinal agents, but have only a limited application in the colour industry. The last portion of the coal tar distillation, the so-called “anthracene oil,” is a thick, buttery, greenish mass, which contains anthracene, phenanthrene, methylanthracene, diphenyl, acenaphthene, naphthalene, methylnaphthalene, pyrene, chrysene, retene, fluorene, carbazole, acridine, and other bodies. For the extraction of the anthracene, the oil is cooled, and the anthracene which separates out mixed with other hydrocarbons is freed from the oily mother liquor by pressing or centrifugating. The greenish gray mass thus obtained, which only contains from 10 to 12% of pure anthracene, is then submitted to a pressure of +P) ea 200-300 atmospheres in hydraulic presses heated by steam; by this means a large part of the phenanthrene and naphthalene is removed, and the anthracene value of the product is raised to from 25 to 40°. For further purification the crude anthracene is washed with “solvent naphtha” or with light petroleum spirit, in which the anthracene is more sparingly soluble than the accompanying phenanthrene, etc. The anthracene thus purified usually has a value of from 50 to 60%, and is sufficiently pure for the preparation of anthraquinone. Recently pyridine bases or a mixture of these with “solvent naphtha” have been very successfully employed for the washing of anthracene, as by this means the carbazol is more completely removed, and the value of the product in anthracene is raised to about 807% (of. Ger. Pat. 42053). To obtain chemically pure anthracene the commercial product is ground up with a mixture of caustic potash and lime, and submitted to distillation, after which it is again washed with solvents and finally sublimed. Considering the great number of hydrocarbons, etc., of the aromatic series which coal tar contains, it is remarkable how few are at present employed as raw products in the colour industry. This is largely due to the difficulty of isolating the others (¢.g. methylnaphthalene) in a state of purity; it is probable, however, that the progress of research will enable many of these bodies to be utilised which are at present valueless. Benzene (Senzo/) CegHe Us: 0 Strongly refractive, colourless, mobile liquid. B.p. 80°-5 corr.; m.p. 6°; sp. gr. 4* = -8839. Solidifies at 0° to a mass of white crystals, Dissolves completely in fuming nitric acid with formation of mono- and dinitrobenzene (distinction from “benzine” or “benzoline,” 2e. light petroleum). . Valuation of Commercial “ pure benzol.”—The whole should boil within half a degree of the correct boiling point. It should give no crystalline precipitate on standing with a few drops of phenylhydrazine (carbon disulphide). On shaking with conc. sulphuric acid the latter should only be slightly darkened (thiophene or hydrocarbons of the ethylene series). On shaking with sulphuric acid and a fragment of isatin no blue colour should be produced (thiophene). On treatment with nitrosulphuric acid and distillation with steam, no unnitrated hydrocarbon should be obtained (hydrocarbons of the paraffin series). It should solidify on cooling below 0°. “Crude benzol” is a mixture in varying proportions of benzene, toluene, etc., and is valued according to the range of its boiling point, bemg known as “30s.” “50s.” or “90s. benzol,” according as 30%, 50%, or 90% of the whole distils before the thermometer reaches 100° C, Toluene (7oluo/) CH, C,Hg te. CgH;(CHs) or C) Colourless mobile liquid, which does not solidify at — 20°. B.p. 111°; sp. gr. 13 = -8708. The commercial “pure toluol” should only be slightly darkened on shaking with cone. sulphuric acid, and should boil between 111° and 112°. Xylene (Xy/o/) C.H, 1.6. CHa (CHs)» Coal tar xylene is a mixture of the three isomers :— ya Hy Orthoxylene . ; CO) Liquid. Bp. 142°; mp.— 28. CH, Metaxylene . ee quid. Bip 139" = sp, er. ai 19° == 8665, 3 CH; Paraxylene . O Olea peso + m.p. lo" esp, gr ateld” =-3621. CH According to Levinstein different samples of commercial xylene contain from 2 to 15% of orthoxylene, from 70 to 87% metaxylene, and from 3 to 10% paraxylene, together with from 3 to 10% of hydrocarbons of the paraffin series. Metaxylene, which is technically the most important, can be separated from its isomers by treating the mixture with a limited quantity of sulphuric acid, and hydrolysis of the sulphonic acid formed. Valuation of Commercial Xylol_—The greater part should distil between 135° and 140°. When shaken with sulphuric acid, the latter should only be coloured heht brown. For the estimation of the three isomers and of paraffin hydrocarbons, see Levinstein, J. Soc. Chem. Ind. (1884) 3, 77; Ber. 17, 444. Naphthalene C,H, %.¢. OO Colourless crystalline solid. B.p. 218°; mp. 80°; sp. gr. at 15°=1-1517. Volatile with steam. Meadily sublimes, even volatilising slowly at ordinary temperatures. Valuation—The commercial product is almost chemically pure. It should melt sharply at 80° and boil correctly within one degree. Allowed to evaporate in the air it should remain white to the last and leave no residue. No red colour should be produced on heating with cone. sulphuric acid. Dissolved in conc. sulphuric acid, diluted with water, filtered, and the filtrate made alkaline, no smell of pyridine bases should be apparent. No phenols should be extracted by boiling with caustic soda. Anthracene H _ (\-c- Cy,Hiy 42. Bees H Colourless crystalline plates or tables, which when quite pure have a violet fluorescence. B.p. rather over 360°; m.p. 213°. Somewhat sparingly soluble in solvents (alcohol, benzene, etc.). Converted by oxidising agents into anthraquinone. With picric acid in benzene ‘solution it forms the picrate C,,H,,-C,H,(NO,.),OH, which separates in glistening red needles, melting at 170°. Valuation of Commercial Anthracene.—The commercial product contains from 30 to 90% of pure anthracene, the remainder being phenanthrene, carbazol, chrysene, ete. Its value in pure anthracene is determined by weighing the quantity of anthraquinone which it produces on oxidation. 1 g. of the crude anthracene is boiled with 45 g. of glacial acetic acid, and a solution of 15 g. of chromic acid in 10 ac. of glacial acetic acid diluted with 10 cc. of water is slowly run in. After the mixture has been kept boiling for two hours longer it is left till the following day, then diluted with 400 cc. of cold water and filtered after two hours’ standing. The precipitate is washed, first with cold water, then with boiling alkaline water, and finally with boiling water alone, and is transferred to a small porcelain dish and dried at 100°. It is then heated at 100° with 10 @. of slightly fuming sulphuric acid for ie 10 minutes, left till next day in a damp place, and poured into 200 cc. of cold water. The precipitated anthraquinone is filtered off, washed with alkaline water, and finally with hot water alone, then washed into a dish, dried and weighed. The dish is then heated till the anthraquinone has volatilised and is again weighed; the last weight subtracted from the first gives the weight of the anthraquinone, which, multiplied by 85-57, gives the percentage of anthracene in the sample (Luck, Ber. 6, 1347). Phenol (Carbolic Acid) OH C,H;-OH te. O White crystalline solid, consisting of long colourless prisms. B.p. 188° corr. ; m.p. 41° ; sp. er. at 40° = 1-05433. Soluble in 15 pts. of water at ordinary temperatures, the solubility increasing rapidly with the temperature, until at 84° it is miscible in all proportions. An aqueous solution of phenol gives a blue coloration with ammonia and bleaching-powder, a violet coloration with ferric chloride,a yellow coloration with hot nitric acid, and a yellowish precipitate of tribromophenol with bromine water. It is estimated by titration with standard bromine water. Valuation.—The commercial product should melt at about 30°, and boil at about 183° to 186°. It should dissolve completely in aqueous caustic soda. Cresol (Cresylic Acid) C,H,O «e. C,H4(CH,)-OH Coal tar cresol is a mixture of the three isomers :— CHs OH . . Orthocresol O Crystalline solid. B.p. 188°; mp. 31°. CHs Metacresol O Liquid. B.p. 201°; mp. 4°. Paracresol O Prismatic crystals. B.p. 198°; mp. 36°. OH The ortho- and paracresol can be obtained pure from the corresponding ortho- and paratoluidine by treatment in dilute sulphuric acid solution with sodium nitrite, and boiling the diazo compounds, INTERMEDIATE PRODUCTS NITRO COMPOUNDS Nitrobenzene (Nitrobenzol) No, CsH;"NO, te O Preparation—A cold mixture of nitric acid (120 pts. of sp. gr. 1-4) and cone. sulphuric acid (180 pts.) is slowly run into benzene (100 pts.), keeping the temperature below 25° until the greater part of the acid has run in, finally allowing it to rise to 50°. The operation is performed in cast-iron jacketed cylinders provided with mechanical agitators and cooled by a stream of water flowing round them (“nitrators”). After standing the _ nitrobenzene is separated and washed with water. When required quite pure (eg. for per- fumery) it is distilled with steam. The yield is 150 to 152 pts. from 100 pts. of benzene, thus almost theoretical. Properties.—Light yellow liquid of bitter-almond-like smell. Bp. 207°; mp. 4°; spactray. 15> = 1.208. Reactions.—By acid reduction (eg. with iron, and hydrochloric acid) it yields aniline C,H, - NH;. By alkaline reduction (eg. zinc dust and caustic soda) it is converted successively into :—Azoxybenzene C,H,-N,O-C,H,; light yellow needles; mp. 36°. Azobenzene C,H,-N.-C,H,; orange plates; m.p. 68°; bp. 293°. And hydrazobenzene C,H,-N,H,-C,H,; colourless tables; m.p. 131°. The latter when warmed with acids undergoes a molecular ; wa. CoH, - NH, change, and is converted into benzidine | C,H, : NH, Valuation—The commercial product should have the correct specific gravity. It should not contain binitrobenzene (phenylene diamine on reduction), nor unaltered peurege or other hydrocarbons (distillation with steam). m-Dinitrobenzene (Linitrobenzo/) NO, C.H,(NO,).[1 . 3] 1.6. O NO, Preparation—By running a mixture of nitric acid (70 pts. of sp. gr. 1-428) and sulphuric acid (100 pts.) into nitrobenzene (100 pts.) contained in a “nitrator,’ the tem- perature being slowly raised from 70° at the commencement to 100° at the end. The product is separated from the spent acid and washed with hot water. The yield is nearly theoretical. The commercial product consists chiefly of the meta compound, but also contains Leal -small quantities of the ortho and para isomers. Pure m-dinitrobenzene can be readily obtained by crystallising the commercial product from alcohol. Properties—Long yellowish white needles. B.p. 297° corr.; m.p. 89°:8. Slightly — soluble in boiling water, easily in alcohol. Very slightly volatile with steam. Valuation—The commercial product should be light in colour and not contain oil. Warm dilute caustic soda should not extract any nitrophenols. On reduction with tin and hydrochloric acid it should give nearly the theoretical quantity of phenylene diamine, shown by titration with a standard solution of diazobenzene chloride. o- and p-Nitrotoluene (JVitrotoluol) C,H.(CHs)NO» CHs3 NO, : Orthonitrotoluene O Liquid. B.p. 223°; sp. gr. at 24°=1-163. CH, ‘ Paranitrotoluene O Colourless prisms. B.p. 238°; mp. 54°. NO, Preparation—The two isomers are formed simultaneously by nitrating toluene. A mixture of nitric acid (105 pts. of sp. gr. 1-4) and sulphuric acid (175 pts.) is slowly run into toluene (100 pts.) contained in a “ nitrator,” keeping the temperature below 20°. The product is separated and washed with water. The yield is about 142 pts. from 100 pts. of toluene. It usually consists of about 35% para-, 63% ortho-, and 2% meta-nitrotoluene. It is either employed direct, or the para- and ortho-nitrotoluene are separated by fractional distillation (best under diminished pressure). The distillation is stopped when 407% has distilled, the distillate being then nearly pure orthonitrotoluene. The residue on cooling gives crystals of paranitrotoluene which are freed from oil by centrifugating. Reactions. o- and p-nitrotoluene are converted into o- and p-toluidine (¢.v.) by acid reducing agents. By alkaline reduction (eg. zinc dust and caustic soda) o-nitrotoluene gives successively azoxytoluene C,H,(CH,)-N,O-C,H,(CH,), azotoluene C,H,(CH;)- N,-C,H,(CH,), and hydrazotoluene C,H,(CH,)-N.H,-C,H,(CH;), the latter of which is converted into . 4. _ OsH;(CH;) - NH; ; : tolidine | when boiled with acids. CsH,(CH,) - NH, Valuation.—Crude nitrotoluene should boil between 220° and 240°, and should have the sp. gr. 1-167 at 15°. a- or m-Dinitrotoluene (Binitrotoluol) CH, NO, CsH,(CH3)(NO,),[1:2:4] ae Preparation.—By further nitration of nitrotoluene with hot nitrosulphuric acid in the same way as given for dinitrobenzene. From the solid product about 7% of oil is separated by centrifugating, which contains the isomeric dinitrotoluene C,H,(CH;)(NO,),[1:2:6], together with m-nitrotoluene, ete. Properties.—Long yellowish needles. M.p. 60°. Valuation.—In the same way as dinitrobenzene. a-Nitro-m-xylene (Nitrovylol) CH; C,H,(CH;),.NO,[1:3:4] 4.¢. Preparation.—By nitration of m-xylene, or together with several other isomers by nitration of crude xylene. A mixture of 90 pts. of nitric acid (sp. gr. 1-4) and 150 pts. of sulphuric acid is run into 100 pts. of xylene, with rapid agitation, keeping the temperature below 17° until most of the acid has run in, Properties—Light yellow liquid. B.p. 245° corr.; sp. gr. at 17°=1-126. The commercial product is usually a mixture of isomers containing nitro-m-xylene as chief constituent. It is employed without separation for the preparation of xylidine. a-Nitronaphthalene NO, C,)H,-NO, 1.€. ee Preparation.—Finely ground naphthalene (250 pts.) is slowly sprinkled through a sieve into a mixture of nitric acid (200 pts. of sp. gr. 1-375), conc. sulphuric acid (200 pts.), and spent acid from previous nitrations (600 pts.). The operation is performed in a “nitrator” with rapid agitation, and the temperature is kept at 45° to 50°. When cold the waste acid is separated from the cake of nitronaphthalene, and the latter is washed with hot water. If required quite pure it is melted with +1, of its weight of “solvent naphtha,” filtered, and the cake of crystals which is formed on cooling is submitted to hydraulic pressure (Witt, Chem. Ind. 10, 215). Properties—Long fine yellow needles. B.p. 304°: mp. 61°; sp. gr. at 4°=1-331. Readily soluble in alcohol, benzene, etc. a-Dinitronaphthalene NO, CH (NOs). the. OO No, Preparation — By further nitration of a-nitronaphthalene. Properties—Y ellowish needles, M.p. 216°. Sparingly soluble in ordinary solvents, m-Nitraniline NH, H,(NO,)NH[1:3] ie. O 6t44 No, Preparation—By partial reduction of m-dinitrobenzene, either with iron and hydro- chloric acid, or with alcoholic ammonium sulphide. It is also formed together with para- nitraniline by nitration of aniline dissolved in a large excess of cold conc. sulphuric acid, Properties—Long yellow needles or rhombic crystals. Bp. 285°; mp. 114°. Dissolves in 600 pts. of water at 18°. Is volatile with steam. C p-Nitraniline NH, O,H,(NO,)NH,[1:4] te. NO, Preparation.—By slowly adding a mixture of nitric acid (59 pts. of sp. gr. 1-478) and conc. sulphuric acid (120 pts.) to a cooled mixture of acetanilide (100 pts.) dissolved in cone. sulphuric acid (400 pts.). After standing the product is poured into water and the pre- cipitated nitracetanilide C,H,(NO,)NH - CO-CH, is converted into p-nitraniline by boiling with hydrochloric or dilute sulphuric acid (Nolting and Collin, Ber. (1884) 17, 262). Properties—Yellow needles or prisms. M.p. 147°. Dissolves in 1250 pts. of water at 18°. Not volatile with steam. p-Nitro-o-toluidine CH, NH, C,H,(CH,)(NH,)(NO,)[1:2:4] ae. NO, Preparation—By slowly running a cold mixture of nitric acid (1 mol.) with twice its weight of conc. sulphuric acid into a solution of orthotoluidine (1 mol.) in 10 times its weight of sulphuric acid, cooled to 0° in a freezing mixture. The mixture is poured into water and the base precipitated by neutralisation with sodium carbonate (Nolting and Collin, ibid.). In addition to the p-nitro-o-toluidine, which constitutes about 757% of the crude product, about 20% of o-nitro-o-toluidine C,H,(CH;)(NH,)(NO,)[1:2:6] and 3 or 4% of m-nitro-o-toluidine C,H,(CH;)(NH,)(NO,)[1:2:5] are also formed (Green and Lawson, J. Chem. Soc. 1891, 1013). The p-nitro-o-toluidine is obtained pure by crystallisation from water. Properties.—Orange prisms, having an intensely sweet taste. M.p. 107°-5; bp. about 310°. Dissolves in 100 pts. of boiling water. Slightly volatile with steam. SULPHONIC ACIDS OF HYDROCARBONS Benzenemonosulphonic Acid CoH, - SO,H Preparation.—By heating benzene with an equal volume of conc. sulphuric acid with an inverted condenser for 20 to 30 hours (Michael and Adair, Ber. 10, 585). Properties.—Fine deliquescent needles or large tables. M.p. 40° to 42°. m- and p-Benzenedisulphonic Acid 50,1 SO,H C,H,(SO3H), [1:3] & [1:4] ae. and $0,H SO,H Preparation.—A mixture of these two acids is formed by heating benzene with fuming sulphuric acid (Bindschedler and Busch, Mon. Scien. 1878, 1169). It is employed without separation for the preparation of resorcinol, as the latter is formed from both isomers on fusion with soda. Properties.—The potassium salt of the meta acid is less soluble than that of the para acid. Naphthalenemonosulphonic Acids C,H, - SO;H | Two isomeric monosulphonic acids are formed by the action of conc. sulphuric acid upon naphthalene. At a low temperature, 80° and under, the product consists chiefly of the a-sulphonic acid ; at high temperatures, 170° to 200°, the chief product is the B-sulphonic acid ; at intermediate temperatures mixtures of these two acids are formed. They are employed in large quantities for the preparation of a- and 8-naphthol. a-Naphthalenesulphonic Preparation.—By heating naphthalene (4 pts.) with cone. acid sulphuric acid (3 pts.) at 80° for 8 or 10 hours (Merz, Ber. 8, S0,H 126). Or better by stirring finely powdered naphthalene (1 pt.) into cone. sulphuric acid (2 pts.) at 40° and keeping at this temperature for several hours (Landshoff and Meyer, Ger. Pat. 50411). The melt is dissolved in water, filtered from unsulphonated naphthalene and the sodium sulphonate precipitated by the addition of salt. Properties,—Deliquescent crystals. M.p. 85° to 90°. On heating it is converted into the @-sulphonic acid. Its salts are more soluble than those of the §-acid. 8-Naphthalenesulphonic Preparation—By heating naphthalene (1 pt.) with cone. acid sulphuric acid (1 pt.) for several hours at 180°. The product S0.H is dissolved in water, filtered from a little dinaphthylsulphone, OO ; and the sodium salt precipitated by the addition of salt. Properties. —Non-deliquescent plates. Naphthalenedisulphonic Acids OH ¢(SO3H), The following isomers are of technical importance :— Naphthalene- Preparation.—By adding finely powdered naphthalene disulphonic acid (1:5) (1 pt.) to fuming sulphuric acid of 30% SO, (4 pts.), keeping (Armstrong's $-acid) the temperature as low as possible. The product is dissolved S0,H in 3 or 4 times its weight of water or salt solution, when the free acid or its sodium salt separates out, and any isomers formed simultaneously remain in solution (Armstrong, Ler. SO3H 15, 205; Ewer and Pick, Ger. Pat. appl. E. 2619°), Properties—Glistening white plates. Its chloride C,,H,(SO,Cl), melts at 183°, and when heated with phos- phorus pentachloride yields dichloronaphthalene of m.p. 107°. Naphthalene- Preparation—By sulphonation of sodium 8-naphthalene- disulphonic acid (1:6) sulphonate (1 pt.) with fuming sulphuric acid of 257% SO, (Ewer and Pick’s acid) (2 pts.) at a low temperature (Ewer and Pick, Ger. Pat. S0.H 45229%), Properties—Long white hygroscopic needles. Its sodium HO;S salt forms crystalline aggregates (+8H,O). Its chloride yields dichloronaphthalene of m.p. 48°. { tau Naphthalene- Preparation—lIs formed together with the (2:6) and (2:7) disulphonic acid (1:7) isomers by sulphonating naphthalene with cone. sulphuric acid (Armstrong's y-acid) at 160° (Armstrong, J. Chem. Soc. 1881, 133; Ber. 15, 204). 30.1 Properties.—Its chloride melts at 125° and by heating with HO,S : phosphorus pentachloride is converted into dichloronaphthalene of mp. 62°. Naphthalene- Preparation—Together with the (2:7) acid by heating disulphonic acid (2:6) naphthalene (1 pt.) with conc. sulphuric acid (5 pts.) at 160° to (Ebert and Merz’s B-acid) 180° for 4 hours. When the mixture is heated at 180° for S0.H 24 hours, the (2:6) acid is almost the sole product (Ebert AGG ; and Merz, Ber. 9, 592). Properties—Plates. Its sodium salt forms needles ( + H,0). The chloride melts at 226°, and by heating with phosphorus pentachloride is converted into dichloronaphthalene of m.p. 135°. Naphthalene- Preparation—Together with a small quantity of the disulphonic acid (2:7) preceding acid by heating naphthalene (1 pt.), or better (Ebert and Merz’s a-acid) -naphthalenesulphonic acid, with cone. sulphuric acid (5 pts.) HO,$ 80,H for a short time at 160° (Ebert and Merz, Ber. 9,592). It is OO separated from the (2 : 6) acid by adding salt to the hot solution of the mixed calcium salts, when the calcium salt of the (2 : 6) acid is precipitated whilst the calcium salt of the (2:7) acid remains in solution (Landshoff and Meyer, Ger. Pat. 48053°*). Properties.—Deliquescent pointed needles. Its sodium salt forms large needles (+6H,O). The chloride melts at 162°, and by heating with phosphorus pentachloride is converted into dichloronaphthalene of m.p. 114°, Naphthalenetrisulphonic Acid C,9H;(SO3H); A naphthalenetrisulphonic acid is obtained by heating naphthalene (1 pt.) with fuming sulphuric acid (6 to 8 pts.) at temperatures varying between 80° and 180° (Giirke and Rudolph, Eng. Pat. 15716*). The product is probably a mixture of which the (1 : 3: 6) acid forms the chief constituent. Naphthalenetetrasulphonic Acid CioHy(SO3H)4 A naphthalenetetrasulphonic acid is obtained by heating naphthalene (1 pt.) with fuming sulphuric acid of 40°%/ SO, (5 pts.) at 150° for 9 to 10 hours (Bayer and Co. Ger. Pat. 4089 3%). CARBOXYLIC ACIDS OF HYDROCARBONS Benzoic Acid (Benzenemonocarboxrylic Acid) CO,H CeH;-CO,H ave, Preparation.—The mixture of benzylidenedichloride C,H,- CHCl, and benzotrichloride C.H,- CCI, formed by chlorinating toluene, or the high boiling fractions obtained as a by-product in the preparation of benzylchloride (q.v.), are heated with the calculated quantity of milk of lime under a pressure of 4 to 5 atmospheres. The benzaldehyde formed is distilled off with steam and the calcium benzoate remaining is decomposed by hydrochloric acid. The precipitated benzoic acid is filtered off, dried, and sublimed. Properties—White needles or plates. M.p. 121°; bp. 249° corr. Soluble in hot water, sparingly in cold (1 pt. in 500 pts. at 10°). Tolerably volatile with steam. Its salts are easily soluble. Valuation—The commercial product (when made from toluene) usually contains chlorobenzoic acid, which can be estimated by ignition with fusion mixture and precipitation as silver chloride; the quantity should only be small. The benzoic acid should have the right melting point, and dissolve completely in boiling water. It should give correct numbers on titration with normal alkali. Phthalic Acid (0- Benzenedicarboxylic Acid) O,H,(CO,H),[1:2] ae. Osos Preparation.—By oxidation of naphthalene, naphthol, or dinitronaphthol, by dilute nitric acid or chromic acid mixture. The product is purified by sublimation of the anhy- dride (Liiddens, Chem. Ztg. 15, 585; Fuchs, Chem. Ztg. 15, 735). Properties—Rhombic plates. Mp. 213°. Readily decomposes on heating into phthalic anhydride and water. Not volatile with steam. Very sparingly soluble in water, insoluble in chloroform. Its alkaline salts are easily soluble in water. Anhydride Ga, > 0. Very long white needles or prisms. Mp. 128°; bp. 284° corr. Slightly soluble in water, readily in alcohol. The commercial product is chemically pure: it should be quite white, have the right melting point, and dissolve in benzene to a clear solution. Dichlorophthalic Acid and Anhydride CHO, <0 and O,H,Cl.0 Preparation.—By oxidation of dichloronaphthalene tetrachloride C,,H,C1,Cl, with nitric acid (Faust, Ann. 160, 64; Castehaz, Eng. Pat. 447%). Properties—The acid forms thick prisms, soluble in hot water. The anhydride melts at 187°. Tetrachlorophthalic Acid and Anhydride OCLC Ht and) 0,0,<45>0 Preparation.—(1) By passing a stream of chlorine for several hours through a mixture of phthalic anhydride (1 pt.) and antimony pentachloride (6 pts.) heated to 200°. When the reaction is finished the antimony pentachloride is first distilled off, and then the tetra- chlorophthalic anhydride (Gesellsch. f. Chem. Industrie, Ger. Pat. 32564°; Gnehm, Am. Pat. 322368; Ann. 238, 320). (2) By passing a stream of dry chlorine into a mixture of phthalic anhydride (20 pts.), fuming sulphuric acid of 50 to 607% SO, (60 pts.), and iodine (1 pt.), keeping the temperature at about 60° at the commencement, and finally raising it to 200°. The product is poured into cold water, keeping the temperature below 50°, and the tetrachlorophthalic anhydride which separates is filtered off, washed and dried (Juvalta, Ger. Pat. 50177). Properties—The acid forms plates or tables, easily soluble in hot water, sparingly in cold. The anhydride forms long prisms of m.p. 252° corr., insoluble in cold water. Cinnamic Acid (Phenylacrylic Acid) C.H;- CH : CH - CO,H Preparation—(1) By heating benzylidenedichloride (1 pt.) with anhydrous sodium acetate (2 to 3 pts.) for several hours at 180° to 200° (Bad. Anil- und Sodafabrik, Eng. Pat. 3330%, (2) By the action of sodium hypochlorite or hypobromite upon benzylideneacetone C,H, :CH:CH - CO- CH, formed by the condensation of benzaldehyde and acetone in presence of dilute caustic soda (Meister Lucius and Briining, Eng. Pat. 3218*!; Am. Pat. 276888). Properties.—Fine needles or large prisms. M.p. 133°; bp. 300°. Sparingly soluble in water. By nitric acid it is converted into a mixture of o- and p-nitrocinnamic acid. PRIMARY AMINES AND THEIR SULPHONIC AND CARBOXYLIC ACIDS Aniline (Amidobenzene or Phenylanine) NH, C.Hs . NH, Ue é O Preparation—By reduction of nitrobenzene with iron and hydrochloric acid. In a large iron still provided with a mechanical agitator and a condenser, are put 500 pts. of nitrobenzene and 800 pts. of water. The mixture is raised to the boil by blowing in steam and 16 to 20 pts. of hydrochloric acid are added. The steam is shut off and 500 to 600 pts. of finely ground cast-iron borings (“swarf”) are slowly added during several hours. A vigorous reaction takes place, and water nitrobenzene and aniline distil over and are contin- ually returned to the still. When all the iron has been added steam is blown in and the distillate is returned as long as it is yellow. When quite colourless it is collected and the distillation is continued as long as any aniline comes over. On leaving the distillate to stand the aniline sinks to the bottom and is drawn off and rectified. The water contains 3% of aniline, and is employed to raise steam for blowing over the aniline in a subsequent operation. The yield is about 70% of the nitrobenzene employed or 106% of the ben- zene, ie. about 90°/ of the theoretical yield. Properties. —Colourless refractive oil of peculiar smell. B.p. 182°; mp. 8°; sp. gr. at 15°=1-0275. It is soluble in about 32 pts. of water at 15°, and dissolves 5’/ of water at the same temperature. Readily volatile with steam. Valuation.—Commercial “pure aniline” should have the specific gravity 1-0275 at 15°. When distilled in a fractionating flask, with the thermometer in the vapour, 907/ of it should boil correctly within half a degree. It should dissolve clear in dilute hydrochloric acid. The presence of a trace of nitrobenzene is shown by the oil having a yellow tint. “ Aniline for red” is a mixture of aniline, orthotoluidine, and paratoluidine, and is either made by mixing the constituents or by nitration and reduction of a mixture of benzene and toluene (“ heavy benzol”); it should boil between 190° and 200° and have the specific gravity 1-007 to 1-009 at 15°. Derivatives.—By boiling aniline with an equal weight of glacial acetic acid for 48 hours it is converted into acetanilide C,H,- NH - CO - CH,, a white crystalline solid which boils at 295° and melts at 115°. Aniline heated with chloracetic acid yields phenylglycocol C,H, - NH . CH, - CO,H, a body which has recently become of importance for the preparation of artificial indigo; it forms colourless crystals which melt at 127°. The sulphonic acids of aniline are described as “sulphanilic acids,” the carboxylic acids as “amidobenzoic acids” (g.v.). p-Sulphanilic Acid NH, C,H,(NH,)SO,H[1 : 4] ice. SO,H Preparation —Acid sulphate of aniline C,H,-NH,,H,SO, obtained by mixing 100 pts. of aniline with 105 pts. of cone. sulphuric acid, is heated on trays in an oven at 180° to 220° until aniline can be no longer detected on boiling a sample with caustic soda (Neville and Winther, Ber, 13, 1940). Properties.—Crystallises from water in large colourless rhombic plates (+ H,O). Spar- ingly soluble in cold water, more easily in boiling water. By nitrous acid it is converted into p-diazobenzenesulphonic acid CsH, eed Its salts are easily soluble. m-Sulphanilic Acid NH, C,H,(NH,)SO;H[1 :3] ie. SO,H Preparation—By reduction of m-nitrobenzenesulphonic acid. Nitrobenzene is mixed with 3 times its weight of fuming sulphuric acid (207% SO;) and then heated for 5 hours at 60° to 70° adding more anhydrous sulphuric acid until the product is soluble in water. The mixture is then poured into 4 times its weight of water, reduced by adding the requisite quantity of iron, made alkaline with lime, filtered, and the calcium salt converted into sodium salt by sodium carbonate (Limpricht and Bernthsen, Ann. 177, 82). Propertves—Small colourless needles. Tolerably soluble in water. Forms easily soluble salts. By nitrous acid it is converted into m-diazobenzenesulphonic acid. o-Amidobenzoic Acid (Anthranilic Acid) NH. CO,H C.H,(NH,)CO,H [1:2] te. O Preparation.—By oxidation of acetyl-o-toluidine with potassium permanganate and saponification of the acetamidobenzoic acid formed. Also by reduction of o-nitrobenzoic acid formed by oxidation of o-nitrotoluene with potassium permanganate. Properties—Colourless plates. M.p. 145°. Easily soluble in water and alchohol. Derwative—By the action of chloracetic acid it is converted into phenylglycocol- carboxylic acid C,H,(CO,H)-NH-CH,-CO,H, which has recently been employed for the pro- duction of artificial indigo. m-Amidobenzoic Acid NH, Preparation—By reduction of m-nitrobenzoic acid formed by nitration of benzoic acid (Gerland, Ann. 91, 188). Properties—Small needles. M.p. 174°. Sparingly soluble in cold water, more easily in hot. [ 16 ] Phenylhydrazine-p-sulphonic Acid NH. NH, CeH,(NH - NH,)SO;H[1:4] i.e. SO;H Preparation.— By reduction of diazobenzenesulphonic acid CHi (from p-sul- phanilic acid) with a warm solution of sodium sulphite, and boiling the product with hydro- chloric acid (Fischer, Ann. 190, 74). Also by sulphonation of phenylhydrazine or of phenylhydrazine sodium sulphite with 5 or 6 pts. of cone. sulphuric acid at 100°. Properties.—Colourless needles (+4H,O). Sparingly soluble in cold water, easily in hot. Its alkaline salts are easily soluble. o-Toluidine OH; NH, C,H,(CH;)NH, {1 : 2] LCs O Preparation.—By reduction of o-nitrotoluene, or together with p-toluidine by reduction of crude nitrotoluene. The reduction is performed in exactly the same way as given for aniline, the yield being about 73% of the nitrotoluene employed. When unseparated nitro- toluene is used, the fluid toluidine obtained is a mixture of about 63% orthotoluidine, 357 paratoluidine, and 2% metatoluidine. This is either employed direct (eg. for “aniline for red”) or is separated more or less completely by various methods, e.g. freezing out paratolui- dine hydrate ; fractional neutralisation with oxalic, phosphoric, or sulphuric acids; fractional sulphonation, etc. (Ger. Pats. 37932° and pce Eng. Pat. 3111%), Properties—Colourless oily fluid. B.p. 197°; sp. gr. 1:0037 at 15°. Volatile with steam. Valuation.—The presence of aniline is detected by the production of a violet colour on shaking the ethereal solution with aqueous chloride of lime. For the estimation of para- toluidine in commercial fluid toluidine various methods have been proposed, none of which however can claim to be more than approximately accurate (Rosenstiehl, B/. 17, 7; Schoop, Chem. Ztg. 1887, 1223; Lunge, Chem. Ind. 1885, 74; Hiusermann, Chem. Ind. 1887, 56). The best method appears to be that of Merz and Weith (Ber. 2, 433), which is performed as follows :—10 e.c. of the oil, which has been dried over solid caustic potash, is heated with 10 ce. of acetic anhydride for 2 hours at 140°, the product is mixed with 350 c.c. of acetic acid and poured into 800 cc. of cold water. After standing for two days the separated paracettoluide is filtered off, washed with dilute acetic acid (10%), dried, and weighed. From this weight the percentage of paratoluidine is calculated, since 100 pts. of paracettoluide correspond to 71-8 pts. of paratoluidine. Commercial “pure orthotoluidine” should give no precipitate when tested in this way. “Fluid toluidine” should boil within two degrees, and have a specific gravity of -9995 to 1-0005. It should dissolve clear in dilute hydro- chloric acid. p-Toluidine CH; CeH,(CH;)NH,[1:4] we. NH, Preparation—By reduction of paranitrotoluene with iron and hydrochloric acid, or ny separation from fluid toluidine (v. supra). eh | Properties.—Colourless plates of peculiar smell. B.p. 198°; m.p. 45°. Only slightly soluble in cold water; a solution in warm water deposits the crystalline hydrate C,H,NH,,H,O on cooling. Valuation—The commercial product should melt and boil correctly. It should not contain oil or water. o-Toluidine-m-sulphonic Acid CH; NH, CgH,(CH;)(NH,)S03H [1:2:5] te. ) HO,S Preparation.—By heating acid sulphate of orthotoluidine C,H,NH,,H,SO, in an oven at 180° to 200° for several mathe Properties—Rhombic tables or prisms (+H,O). Sparingly soluble in cold water, easily in hot. p-Toluidinesulphonic Acids CeH;(CH;)(NH.)S03H [1 :4:2] and [1:4:8] Preparation. A mixture of these acids is formed on heating paratoluidine with fuming sulphuric acid or by baking eG acid sulphate. In the latter case the [1:4: 2] acid is the chief product. Properties,—The [1 : 4:2] acid is insoluble in alcohol, sparingly soluble in cold water, and crystallises in rhombohedra. The [1:4:3] acid is tolerably soluble in cold water, readily in alcohol, and crystallises in needles. a-m-Xylidine (Amido-m-xylene) OH, C,H,(CHs),.NH,[1:3:4] «we. On NH Preparation—By the reduction of Sry aieeeeie with iron and hydrochloric acid. The commercial xylidine obtained by nitration and reduction of the unseparated xylene contains about 50°% of this isomer, which can be separated from the mixture more or less completely by neutralising with acetic or hydrochloric acid and pressing and_basifying the cake of acetate or hydrochloride which is formed. Usually, however, the crude xylidine is used for the preparation of scarlet without any separation (cf. Eng. Pat. 11822°%°), Properties.—Colourless oil. B.p. 215° corr.; sp. gr. at 15° = -9184. Valuation—Commercial xylidine should distil to the extent of 907% between 210° and 217°. The presence of hydrocarbons is detected by dissolving in hydrochloric acid. p-Xylidine (Amido-p-xylene) O,H,(CH,),NHe[1:4:2] ae. CH, Preparation.—By nitration and reduction of paraxylene (Nolting and Forel, Ber. 18, 2680). Occurs in commercial xylidine. Properties—Colourless oil. B.p. 221°; sp. gr. at 15° = -980. D [f 18 ] Xylidinesulphonic Acid CgH,(CH;).(NH,)SO3H Preparation—A mixture of isomeric sulphonic acid is obtained by heating commercial xylidine (120 pts.) with fuming sulphuric of 207/50, (400 pts.) at 80° to 100°. On pouring the product into cold water the sparingly soluble sulphonic acid of metaxylidine O,H,(CH,),(NH,)SO,H[1:3:4:6] separates out, whilst from the mother liquor, by conver- sion into sodium salts and concentrating, the sodium p-xylidine sulphonate C,H,(CH,),(NH,) SO,H [1:4:2:5] crystallises out on cooling (Witt, Ger. Pat. 34854). Properties.—The metaxylidine sulphonic acid forms sparingly soluble flat prisms ; its sodium salt is easily soluble. The paraxylidine sulphonic acid forms easily soluble pearly plates; its sodium salt is sparingly soluble. w-Cumidine OH, OH, C,H,(CH3;)3N H, {1 72; 4 : 5] 4G, HN CH, Preparation.—By heating the hydrochloride of paraxylidine or commercial xylidine with methyl alcohol at 300° (Eng. Pat. 3997*). Properties—Colourless crystals. Bp. 236°; mp. 62°. a-Naphthylamine (a-Amidonaphthalene) NH, C,H, NH, 40. OO Preparation.—By reduction of a-nitronaphthalene with iron and hydrochloric acid. An iron vessel provided with an agitator is charged with 800 pts. of iron-borings, a little water, and 40 pts. of hydrochloric acid, and gently warmed: 600 pts. of granulated nitro- naphthalene are then slowly added, keeping the temperature at about 70° to 80°. When all has been added the temperature is maintained for 5 or 6 hours by blowing in steam, until the whole of the nitronaphthalene is reduced. The mass is then mixed with milk of lime (from 50 pts. of lime) and emptied out. The mixture is spread out on iron trays, which are placed on shelves in an iron retort. The latter is strongly heated and a current of super- heated steam is passed through until no more naphthylamine distils over. The naphthyl- amine is condensed in a worm surrounded with warm water, separated from water, dried, and rectified from an iron retort. The yield is fairly good, though considerably below the theoretical (Witt, Chem. Ind. 10, 215). Properties—F lat colourless needles or plates. B.p. 300°; m.p: 50°. Nearly insoluble in water. Disagreeable smell. Valuation.—The commercial product forms grayish-white or brownish erystalline lumps. It should melt nearly correctly, and only leave a trace of naphthalene ete. on solution in dilute hydrochloric acid. [ 19 ] a-Naphthylaminemonosulphonic Acids CypH,(NH,)SO,H Of the seven possible monosulphonic acids of a-naphthylamine the following have at present found technical application :— a-Naphthylaminesulphonic acid (1: 4) (Piria’s naphthionic acid) NU, S0,H a-Naphthylaminesulphonic acid L, (1: 5) (Lawrent’s naphthalidunie acid) NH, SO,H a-Naphthylaminesulphonic acid (1 : 6) (Cleve’s B-acid) NH, 06 a-Naphthylaminesulphonic ~ acid Sch, (1: 8) (Schéllkopf acid) HO;S NH, a-Naphthylaminesulphonic acid (1: 2) NH, oo Preparation—(1) By baking a mixture of equal mols. of a-naphthylamine and sulphuric acid at 180° to 200°. (2) By heating a-naphthylamine (1 pt.) with cone. sulphuric acid (4 or 5 pts.) at 100° to 110°. Properties.—Small colourless needles. Very sparingly sol- uble in water (1 pt. in 4000 at 15°). Its sodium salt forms large colourless crystals (+ 4H,0), easily soluble in water, insoluble in alcohol. Its diazo compound is white. Preparation.—(1) By adding a-naphthylamine hydrochloride to fuming sulphuric acid (207/SO,) in the cold (Witt, Ber. 19, 578). (2) By reduction of the mixed nitronaphthalenesulphonic acids, obtained by nitration of a-naphthalenesulphonic acid, and separation from the (1:8) acid, which is formed simul- taneously, by the greater solubility of its sodium salt (Schollkopf Anil. Co., Eng. Pats. 15775® and 15782%, Properties.—Microscopic needles; 1 pt. of the acid is soluble in 950 pts. of water at 15°; in hot water it is tolerably easily soluble. Its sodium salt is soluble in alcohol. Its diazo com- pound is yellow. Preparation.—By nitration and reduction of @-naphthalene- sulphonic acid (Cleve, B/. 26, 444); or together with the (1:5) acid by long heating of a-naphthylamine (1 pt.) with cone. sulphuric acid (5 pts.) at 125° to 130° (Hirsch, Ber, 21, 2371; Erdmann, Ann. 275, 192). Propertves.— Plates or needles. 1 pt. dissolves in 1000 pts. of cold water. Preparatwon.—By nitration and reduction of a-naphthalene- monosulphonic acid; it is separated from the preceding acid, which is formed simultaneously, by conversion into the sodium salts, that of the (1:8) acid being the least soluble (Schollkopf Anil. Co., Eng. Pats. 15775 and 15782"; Am. Pat. 333034; H. Erdmann, Ann. 247, 318). Properties—White needles. 1 pt. dissolves in 4800 pts. of water at 21°,in 240 pts. at 100°. Its diazo compound erystallises in greenish-yellow prisms, which on heating with water are readily converted into the sultone ©,H,< $0, => (ias} Preparation By heating sodium naphthionate at 200° to 250° (Landshoff and Meyer, Eng. Pat. 6195%; Cleve, Ber. 24, 3472; Erdmann, Ann. 275, 225). Properties.—Small glistening needles. Tolerably soluble in water (1 pt. in 225 at 15°). Its sodium salt forms small scales much less soluble than sodium naphthionate (1 pt. in 60 pts. of cold water). a-Naphthylaminedisulphonic Acids C,H, (NH,)($0,H), The following are technically important :— a-Naphthylamine- disulphonic acid ¢« (1:3: 8) HO,S NH, SO,H (Constitution : Bernthsen, Ber, 22, 3328) a-Naphthylamine- disulphonic acid 6 or Sch. (1:4: 8) HO,S NH, SO,H (Constitution : Armstrong and Wynne, Proc. Chem. Soe. 1890, 126) a-Naphthylamine- disulphonic acid (1:4: 6) (Dahl's acid IT.) NH, HO.$ SO,H (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1890, 126) Preparation.—(1) Together with the 6-acid by nitration and reduction of the mixture of the (1: 5) and (1 : 6) naphthalenedi- sulphonic acids obtained by sulphonating naphthalene with sul- phuric anhydride at the ordinary temperature; it is separated from the é-acid by the greater solubility of its sodium salt (Actien- ges. f. Anilinfabrikn., Eng. Pats. 4625%° and 59108; Am. Pat. 405938). (2) Nitration and reduction of the (1:6) naphthalene- disulphonic acid obtained by sulphonating 6-naphthalenemono- sulphonic acid with fuming sulphuric acid at 100°, or by sulphonating naphthalene with cone. sulphuric acid at 90° to 120° (Ewer and Pick, Ger. Pat. 52724; Bad. Anil. and Soda Fabrik, Ger. Pat. appl. B. 9514; Bernthsen, Ber. 22, 3328). Properties—Colourless glistening scales. Its acid sodium salt forms rather sparingly soluble long needles. Its diazo compound crystallises in small white needles; by boiling with water it is converted into the naphthosultonesulphonic acid e. Preparation.— (1) By heating a-naphthylaminemonosul- phonic acid Sch. (1 pt.) with fuming sulphuric acid of 107% anhydride (3 pts.) at 100° till soluble in water (Schollkopf Anil. Co., Eng. Pats. 15775 and 15782; Am. Pat. 333034). (2) Together with the preceding acid (¢.v.) by nitration and reduction of the mixture of (1:5) and (1:6) disulphonie acids of naphthalene, obtained by sulphonating naphthalene with fuming sulphuric acid at the ordinary temperature. Properties.—The acid sodium salt crystallises in long prisms, the neutral salt in long needles or clear yellow compact crystals (+ 2H,0). The diazo compound on boiling with water yields a-naphthosultonesulphonic acid 6 (Bernthsen, Ber, 23, 3090). Preparation.—Together with the following acid by heating 1 pt. of a-naphthylamine with 4 to 5 pts. of fuming sulphuric acid (25°/SO,) at 120°; or by further sulphonation of naph- thionic acid by the action of 385 pts. of fuming sulphuric acid (25/SO;) upon 1 pt. of naphthionic acid at a temperature below 30° for several days. The mixed acids are converted into calcium salts, and extracted with boiling 85'/ alcohol, when the calcium salt of the acid II. dissolves whilst that of acid III. remains insoluble (Dahl and Co., Ger. Pat. 41957°* ; Erdmann, Ann. 275, 218. Properties—Needles. Easily soluble in hot water, less in cold. Its salts are very soluble. The diazo compound forms _ small silky yellow needles, which give a yellow colouring matter on warming with dilute nitric acid. [ 21 ] a-Naphthylamine- Preparation.—Together with a smaller quantity of acid II. disulphonic acid (1:4:7) by sulphonating a-naphthylamine or naphthionie acid with (Dahl's acid ITT.) fuming sulphuric acid (see above). The calcium salt is left aS NH, undissolved when the mixed calcium salts are extracted with boiling 85% alcohol (Dahl, Ger. Pat. 41957°°; Erdmann, Ann. 275, 218). Properties—Small needles. Sparingly soluble in cold water, easily in hot (1 pt.in 20). The diazo compound is converted into “ Naphthol yellow 8.” on boiling with dilute nitric acid. S0,H (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1890, 17) a-Naphthylamine- Preparation.— By sulphonating a-naphthylaminesulphonic disulphonic acid (1: 2:5) acid (1:2) with fuming sulphuric acid (Landshoff and Meyer, (Landshoff & Meyer’s acid) Eng. Pat. 6195%), NH, Properties.—N ot readily soluble. Its diazo compound forms Probably a: brilliant yellow needles. HO,S | a-Naphthylamine- Preparation.—By heating the salts of a-naphthylaminetri- disulphonic acid (1: 2:7) sulphonic acid (1:2:4:7) with water under pressure at 230° (Kalle’s acid) (Kalle and Co. Ger. Pat. 62634°), NH, Properties.—Fine needles. Its barium salt is very sparingly HO,S SO;H soluble even in hot water. The diazo compound forms easily soluble needles. a-Naphthylaminetrisulphonic Acids CH N H2)(SO3H)s a-Naphthylamine- Preparation—By heating naphthionic acid (1 pt.) with trisulphonic acid (1:2:4:7) fuming sulphuric acid of 407% anhydride (3 to 4 pts.) for Nu, 10 hours at 120° (Meister, Lucius, and Bruning, Ger. Pat. HO,$ 30,H 22545), Properties.—Its diazo compound is converted into “ Naphthol S0;H yellow 8.” on warming with dilute nitric acid. a-Naphthylamine- Preparation.—By nitration and reduction of the naphthalene- trisulphonic acid (1:3: 6:8) trisulphonic acid obtained by direct sulphonation of naphtha- HO.S NH, lene (Koch, Eng. Pat. 9258°°), Properties—Its diazo compound is colourless. HO,S S0,H a-Naphthylamine- Preparation.—By nitration and reduction of the naphthalene- trisulphonic acid (1:3:5:7) trisulphonic acid formed by further sulphonation of the (2: 6) naphthalenedisulphonic acid (Cassella and Co., Eng. Pat. NH, H10,8/\/\" ee | er Coke Properties—Its acid sodium salt and its diazo compound HO,S are sparingly soluble. : 8-Naphthylamine (8-amidonaphthalene) GH, Neer Cee Preparation By heating 8-naphthol (10 pts.) with caustic soda (4 pts.) and ammonium chloride (4 pts.) in an autoclave at 160°. When cold the melt is powdered, and after [ 22 ] extracting unaltered 8-naphthol with aqueous caustic soda, is dissolved in dilute hydrochloric acid, filtered, and the @-naphthylamine precipitated with soda (Bad. Anil. and Soda Fabrik, Ger. Pat. 14612), Properties—W hite pearly plates. hot water, sparingly in cold. B.p. 294°; mp. 112°. Odourless. Soluble in Tolerably volatile with steam. Valuation.—The commercial product forms pinkish-white crystalline lumps, almost odourless. hydrochloric acid. It should melt correctly and only leave a small residue on solution in dilute 8-Naphthylaminemonosulphonic Acids CoHe(N H,)SO,H The following four isomers are employed for the preparation of colours either separately or more or less mixed with one another :— 8-Naphthylamine-a- sulphonic acid (2: 8) (Badische acid) SO,H (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1888, 105; 1889, 53; Witt, b. 21, 3490) 8-Naphthylamine-(- sulphonic acid (2 : 6) (Brénner’s acid) NH, HO,S (Constitution : Armstrong and Wynne, Proc. Chem. Soc, 1889, 51; 1890, 130) 8-Naphthylamine-y- sulphonic acid (2 : 5) (Dahl's acid) NH, SO,H (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1889, 48; 1890, 128) Preparation—(1) Together with the y (about 407), 8 (about 5%), and 6 acid (about 57/) by heating @-naphthylamine (1 pt.) with cone. sulphuric acid (3 to 34 pts.) for 5 or 6 hours at 100° to 105° (Bad. Anil. and Soda Fabrik, Ger. Pat. 20760*). (2) Together with the y-acid (about 70% y and 307% a) by warming §-naphthylamine (1 pt.) with fuming sulphuric acid of 20% SO, (3 pts.) at 85° for a short time (Dahl and Co. Eng. Pats. 7712°4 and 77138). (3) Together with the y-acid (55% y and 45% a) by treating @-naphthylamine (1 pt.) with conc. sulphuric acid (3 pts.) at the ordinary temperature (15° to 20°) for several days (Dahl and Co.). The a-acid is separated from its isomers by extracting the mixed sodium salts with boiling 90°% alcohol, in which the sodium salts of the B-, y- and 6-acids are readily soluble, but not the a-sodium salt. Properties.—Prisms. Very sparingly soluble in water. Its sodium and ammonium salts crystallise in large soluble prisms. Its diazo compound is a sparingly soluble greenish-yellow precipitate. Preparation—(1) By heating @-naphthol-@-sulphoniec acid S. with aqueous ammonia in an autoclave at 180° for several hours (Brénner, Eng. Pat. 3724°?; Am. Pat. 332829). (2) By baking the acid sulphate of 8-naphthylamine at 200° to 210° (Liebmann, Mon. Scien. 1885,1043). (3) Together with about an equal quantity of the d-acid by heating @-naphthylamine sul- phate (1 pt.) with cone. sulphuric acid (3 pts.) at 150° to 160° (Bayer and Duisberg, Ber, 20, 1426; Schultz, Ber. 20, 3158). Properties.—-Prismatic needles or silky plates. Its ammon- ium salt forms very large thin plates with violet fluorescence. Preparation—Together with the a-acid (see above) by sulphonating @-naphthylamine at low temperatures. Separ- ated by the solubility of the sodium salt in boiling alcohol of 90%, which leaves the sodium salt of the a-acid undissolved (Dahl and Co., Eng. Pats. 77128 and 7713%; Green, Chem. Soc. 1889, 35), Properties. — Long white needles. Sparingly soluble in water. Its diazo compound is a microcrystalline greenish- yellow powder. [ 23 ] 8-Naphthylamine-6- Preparation.—(1) By heating f$-naphtholsulphonic acid sulphonic acid (2:7) FF. (q.v.) with 2 pts. of aqueous ammonia (20'/) in an auto- (Bayer’s acid) clave at 250° for six hours (Cassella, Eng. Pat. 12908°; Am. (Cassella’s acid F.) Pat. 362560; Weinberg, Ber. 20, 2907). (2) Together with HO,S NH, the B-acid by heating @-naphthylamine sulphate (1 pt.) with 1) cone. sulphuric acid (3 pts.) at 150° to 160° (Bayer and Co. Eng. Pat. 5646%). The two acids can only be separated with (Constitution : Weinberg, great difficulty. Ber. 20, 2910) Properties. —Long fine needles. More soluble in warm water than the @-acid (separation). The calcium salt forms plates (+ 6H,O) with blue fluorescence. The diazo compound is an orange-red crystalline powder. 8-Naphthylaminedisulphonic Acids CioH(N H2)(SO3H), The following isomers have at present found technical application :— 8-Naphthylamine- Preparation— By heating f-naphthol-disulphonic acid R. disulphonic acid R. or a with aqueous ammonia in an autoclave at 200° to 250° (Duis- Pou: 0) berg and Pfitzinger, Ber. 22, 396). Or by passing ammonia NH, gas over the dry sodium salt heated to 250° (Landshoff, Ger. ACO Pat. 27378*). Properties—Its diazo compound forms sparingly soluble (Constitution : Armstrong small yellow needles. and Wynne, Proc. Chem. Soc. 1890, 12) 8-Naphthylamine- Preparation.—(1) By heating $-naphthylaminesulphate disulphonic acid G. or y (1 pt.) with fuming sulphuric acid of 25% SO, (3 pts.) at 110° 2 0e'8) to 140° (Gans and Co., Eng. Pat. 816°). (2) By long action of S0,H fuming sulphuric acid of 207% SO, upon the a-monosulphonic NH acid at ordinary temperatures (Armstrong and Wynne, Proc. 406 Chem. Soc. 1890, 128). (3) By heating the salts of 8-naphthol- disulphonie acid G,. in a stream of dry ammonia gas for 12 hours at 200° to 250°. Properties.—Both the acid and its salts are easily soluble in water. It does not combine with diazo compounds. (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1890, 12 and 128) 8-Naphthylamine- Preparation.—By heating the @-naphthol-disulphonic acid 6 disulphonic acid 6 (2:3:7) with aqueous ammonia for 12 hours at 200° (Cassella and HO,’ NH, Co., Ger. Pat. 46711). oes Properties.—Sparingly soluble in cold water, readily in hot. (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1890, 127) 8-Naphthylamine- Preparation.—Naphthalenedisulphonie acid (1: 5) is nitrated disulphonic acid C. (2:4:8)in sulphuric acid solution, the mixture poured into salt and SO, water, and the precipitated sodium salt is reduced (Cassella, NH, Ger. Pat. appl. C. 3542). Properties.—Concentric prisms. The alkaline solution has S0;H a deep blue fluorescence. Its diazo compound forms small yellowish needles, rather sparingly soluble. | 24 4 8-Naphthylamine- Preparation. — By sulphonating $-naphthylamine-8-mono- disulphonic acid (2:1:6) sulphonic acid at the ordinary temperature (Armstrong and 30.1 Wynne) or at 110° (Forsling, Ber. 21, 3495). ‘NH, Properties—Small white very soluble needles. TGC (Constitution: Armstrong and Wynne, Proc. Chem. Soc. 1890, 130) SECONDARY AND TERTIARY AMINES AND THEIR SULPHONIC ACIDS. Diphenylamine (CgH;)NH te. GTS Preparation—By heating equal mols. of aniline and aniline hydrochloride in an autoclave for several hours at 200°. The product is boiled with dilute hydrochloric acid to remove unaltered aniline and the diphenylamine which remains insoluble is distilled. The yield is | 60 to 70%. Properties—Monoclinic plates. B.p. 310°; m.p. 54°. Gives a deep blue colour on adding a drop or two of nitric acid to its solution in cone. hydrochloric or sulphuric acid. Is a very weak base, its salts being decomposed by water. Valuation—The commercial product is a yellow crystalline solid of pleasant smell. It should melt tolerably correctly and contain no oil. Methyldiphenylamine (CgHs).NCH; Preparation.—By heating diphenylamine (100 pts.), hydrochloric acid (68 pts.), and methyl alcohol (24 pts.) for 10 hours at 250° in an autoclave (Girard, Bl. 23, 2). Properties—Oil. B.p. 293°; sp. gr. 2°=1-0476. + Benzylaniline CcH;-NH-CH,-C,H; i.e < >NH-CH,C > Preparation.— By heating aniline with benzyl chloride at 160° (Fleischér, Ann. 138, 225). ; Properties—Prisms. B.p. 310°; m.p, 33°. Methylbenzylaniline CsH; - N(CH,) - CH, - O,H, Preparation.—By heating equal mols. of monomethylaniline, benzyl chloride, and aqueous caustic soda at 100° (Nolting, Jahresber, 1883, 702). Properties—Oil. Bp. 308°. Sulphonie acid.—By fuming sulphuric acid at 50° to 60° it is converted into the easily soluble sulphonic acid C,H,. N(CH,) - CH,- C,H,- SO,H. Ethylbenzylaniline C,H, - N(C,H,) - CH, - CoH, Prepared in the same way as the methylbenzylaniline. Oil. B.p. 286° uncorr. at 710 mm. By fuming sulphuric acid at 50° to 60° it is converted into the easily soluble sulphonic acid C,H,-N(C,H,)-CH,-C,H,(SO,H), which is used for the preparation of “ Acid green,” “Thiocarmine R,” “ Formyl violet,” ete. Monomethylaniline NHCH, O,H;-NH(CH,) ie. Preparation.—By heating aniline hydrochloride or a mixture of aniline and hydrochloric acid with rather more than 1 mol. of methyl alcohol at 200°. The product is converted into _ sulphate, and the easily soluble sulphate of methylaniline separated from the sparingly soluble aniline sulphate. The sulphate is basified and fractionated. The commercial product contains 90 to 95% of pure monomethylaniline. Properties.—Colourless oil. B.p. 192°; sp. gr. at 15°=-976. By nitrous acid it is converted into the oily nitrosamine C,H, - N(CH,)(NO), which by the action of alcholic hydro- chlorie acid undergoes isomeric change into the p-nitrosomethylaniline C,H,(NO) - NHCH,. Dimethylaniline C,H, - N(CH,), Preparation.—By heating a mixture of aniline (75 pts.), aniline hydrochloride (25 pts.), and methyl! alcohol (free from acetone) (75 pts.), in a cast-iron autoclave at 230° to 270°. The product is rectified. The yield is about 120 pts. from the above proportions (Schoop, Chem. Zig. 1887, 253; J. Soc. Chem. Ind. 1887, 436). Propertves.—Colourless oil. B.p. 192°; sp. gr. at 15°=-96. Solidifies at +-5° to a crystalline solid. Valuation.—The commercial product is usually nearly pure. It should have the correct specific gravity and distil completely between 190° and 192°. Dissolved in a litle ether and mixed with a drop or two of cone. sulphuric acid it should give no precipitate of aniline sulphate. The presence of monomethylaniline is detected and roughly estimated by mixing 5 cc. of the oil with 5 c.c. of acetic anhydride and observing the rise of temperature: each degree rise indicates about $°/ of monomethylaniline. A more accurate method is to distil off the dimethylaniline and excess of acetic anhydride and weigh the residue of methylacetanilide. A good sample should not contain more than 3 to 1% of monomethylaniline. Deriwatives—By fuming sulphuric acid it is converted into the m-gulphonic acid C,H,N(CH,).-SO;H [1:3]. By the action of nitrous acid on a cold solution of the hydro- chloride, p-nitrosodimethylaniline C,H,(NO) - N(CH,), [1:4] is formed, which crystallises in large green plates of m.p. 92°, volatile with steam. The nitroso compound is reduced by zine dust and hydrochloric acid to p-amidodimethylaniline (dimethyl-p-phenylenediamine) CHAN H,) - N(OH,), [1:4], a base which forms long white needles of m.p. 41° and b.p. 257°, and is easily soluble in water. Iionoethylaniline NHC,H, C,H;:NH(C,H;) 2.¢. Preparation.—By heating aniline hydrochloride or a mixture of aniline and hydro- chloric acid with rather more than 1 mol. of ethyl alcohol at 200°. Properties—Colourless oil. B.p. 204°; sp. gr. at 18°=-954. Its salts are very sol- uble in water. i Lies oe Diethylaniline CoH; - N(C2H5)z Preparation—By heating aniline hydrochloride and aniline with rather more than 2 mols. of ethyl alcohol (see dimethylaniline). The product contains a considerable quantity of monoethylaniline and is usually treated with sufficient ethyl bromide to complete the re- action. It is obtained more readily and in nearly theoretical yield by heating aniline hydrobromide with 24 mols. of ethyl alcohol at 145° to 150° (Staedel, Ger. Pat. 21241°*). Properties—Colourless oil. B.p. 214°; sp. gr. at 18° = -939. : Valuation.—sSee dimethylaniline. It should distil to the extent of 90% between 212° and 214°, Derwatives—By nitrous acid it is converted into p-nitrosodiethylaniline, which forms large green prisms of m.p. 84°, sparingly soluble in water. By reduction with zine dust and hydrochloric acid the nitroso compound yields p-amidodiethylaniline U;H (NH) - N(CH), [12 4} Dimethyl-a-naphthylamine C,H, 3 N(CH), Prepared by heating a-naphthylamine hydrochloride with methyl alcohol at 180°. Oily liquid. Bp. 273° uncorr. (Friedliinder and Welmans, Ber. 21, 3123). Methyl and ethyl-8-naphthylaminesulphonic Acids C,)H,(S0;H)NHCH, and OypH,(SO;H)NHC.H, Prepared from the corresponding 8-naphthylaminesulphonic acids by heating the aqueous solutions of the sodium salts with methyl or ethyl bromide or with sodium methyl or ethyl sulphate (Eng. Pat. 170838). They are employed for the production of cotton colours by combination with diazotised benzidine or tolidine. Phenyl-a-naphthylamine H a0,H,-NH.O,H; a2 eee Preparation—By heating a-naphthol with aniline or aniline hydrochloride at a high temperature. Propertves—Colourless plates or needles. Bp. 335° at 238 mm; mp. 62% Is employed for the preparation of “ Victoria blue.” Phenyl-@-naphthylamine H @CyH,-NH-C,H, te < >—N—- Preparation.—By heating 8-naphthol (6 pts.) with aniline hydrochloride (5 pts.) for 7 or 8 hours at 170° to 190° Also by heating @-naphthol (7 pts.) with aniline (5 pts.) for 10 hours at 200° to 210°. The operation is performed in an open vessel (Ger. Pat. 14612*). The product is boiled with dilute hydrochloric acid to remove unaltered aniline and with caustic soda to remove unaltered naphthol, and the phenyl-8-naphthylamine is dried and distilled. Properties.—Colourless needles or trimetric crystals. B.p.3895°; mp. 108°. Sparinely soluble in cold solvents, easily in hot, with a blue fluorescence. eect p-Tolyl-a-naphthylamine aC,)H, - NH - O,H,(CH,)[1 : 4] Prepared from a-naphthol and paratoluidine in the same way as phenyl-a-naphthylamine (Friedlander, Ber. 16, 2084). Short colourless prisms which melt at 79°. Is used for the preparation of “ Night blue.” p-Tolyl-8-naphthylamine BC, H, - NH - C,H,(CH,) [1 : 4] Prepared from 8-naphthol and paratoluidine in the same way as phenyl-@-naphthyl- amine (Friedliinder, Ber. 16, 2078). Colourless plates of mp. 103°. Sparingly soluble in alcohol. Is used for the preparation of “ Wool black.” Quinoline C,H,N 4 ycig git7 Ué. _n-bn Preparation.—By heating a mixture of aniline (216 pts.), nitrobenzene (144 pts.), glycerine (600 pts.), and sulphuric acid (600 pts.), for a day at about 125°, then at 180° to 200° till the reaction is complete. The mixture is diluted with water, and the excess of nitro- benzene is boiled off; it is then made alkaline with soda, and the quinoline is distilled off and freed from aniline by treatment in acid solution with potassium bichromate or sodium nitrite. The yield is about 70% of the theoretical (Skraup, Mon. f. Chem. 1, 317; Koénigs, Ber. 13, 911). For the preparation of colouring matters it is usually obtained from the basic por- tion of coal tar oils, and contains, in addition to quinoline, quinaldine and isoquinoline on) Gang to the presence of which the formation of some of the derived colours is due. Properties.—Colourless oil. B.p. 238°; sp. gr. at 20°=1-0947. It forms easily sol- uble salts. The picrate crystallises in yellow needles of m.p. 203°. Quinaldine (Methylquinoline) ; —((CH;)=CH CypHyN _2.¢. ] ——-N = CH Preparation.—By boiling a mixture of aniline (100 pts.), paraldehyde (150 pts.), cone. hydrochloric acid (200 pts.), and aluminium or zine chloride (5 pts.), for 4 or 5 hours (Eng. Pat. 956%). Also by melting with zine chloride the condensation product obtained by the action of paraldehyde (5 pts.) upon a cold solution of aniline hydrochloride (8 pts.) in water (16 pts.) (Eng. Pat. 42078). The base is distilled off with steam after making alkaline. The latter method gives the best yield. Properties.—Colourless oil. B.p. 246°. Chiefly used for the preparation of “ Quinoline yellow.” : Carbazole H CeHy es Oakly Numa? cena NH or Oy gHy— Preparation—(1) Occurs in crude anthracene from which it is extracted by boiling with strong aqueous caustic potash until all the water has evaporated. The layer of Ges: anthracene is removed, and the caustic potash is dissolved in water by which the carbazol potassium C,,H,NK which it contains is decomposed and the carbazol separates. It is purified by crystallisation from alcohol or toluene. (2) By boiling thiodiphenylamine GpHj Opie (obtained by heating diphenylamine with sulphur) with copper powder (Goske, Ber. 20, 233). Properties.—Colourless plates or tables. B.p. 351° corr; m.p. 238°. Sublimes readily. Its sulphuric acid solution gives a blue colour with a trace of nitric or nitrous acid. ‘The picrate forms red needles of m.p. 182°, slightly soluble in cold alcohol or benzene, DIAMINES AND THEIR SULPHONIC ACIDS m-Phenylenediamine (m-Diamidobenzene) NH, C,H,(NH,),[1:3] ie. Own, Preparation.—By reduction of m-dinitrobenzene with iron and hydrochloric acid. The operation is performed in a large iron “reducer” (see aniline), which is charged with 200 pts. of dinitrobenzene and 200 pts. of water. The mixture is raised to the boil by blowing in steam, 16 pts. of hydrochloric acid are put in, and then 420 to 450 pts. of finely ground cast-iron borings are slowly added, keeping up a vigorous reaction. When the reduction is complete, sodium carbonate is added until slightly alkaline, boiled up with 800 to 1000 pts. of water, and the solution of the phenylenediamine filtered from the iron sludge, which is again extracted with water. This solution is either used direct (e.g. for Bismarck brown or Chrysoidine), or is neutralised with hydrochloric acid and evaporated. On adding strong caustic soda solution to the concentrated solution of the hydrochloride the base separates as an oil, which rises to the surface and solidifies on cooling. It is purified by dis- tillation. ; Properties.—Colourless crystalline solid which quickly becomes coloured in the air. Bp. 287°; mp. 83°. Easily soluble in water. With sodium nitrite and acetic acid it gives a brown colour, even in very dilute solution, p-Phenylenediamine ( p-Diamidobenzene) NH, CyH,(NH,) [1:4] ie. CO NH, Preparation.—By reduction of p-nitraniline with iron and hydrochloric acid; or of amidoazobenzene hydrochloride dissolved in aniline by a stream of hydric sulphide. Properties—Colourless crystals. Bp. 267°; mp. 140°. Easily soluble in water. By oxidising agents it is converted into quinone. When oxidised in presence of aniline or o-toluidine it yields blue indamines, which on boiling are converted into safranines. Derivatives—The acetyl derivative C,H,(NH,)NH - CO - CH, is formed by careful re- duction of p-nitracetanilide, and crystallises aah water in needles of m.p. 191°. Dimethyl- p-phenylenediamine U,H,(NH,) - N(CH,), [1:4], see under dimethylaniline. . Wee ae m-Tolylenediamine (Diamidotoluene) CH, NH, C,H,(CH;)(NHp).[1:2:4] ie. Ni, Preparation.—By reduction of m-dinitrotoluene with iron and hydrochloric acid in the same way as m-phenylenediamine (q.v.). The base crystallises from the strong aqueous solution in large prismatic crystals. Properties.—Rhombic prisms. B.p. 280°; mp. 99°. Easily soluble in hot water. With nitrous acid it reacts like m-phenylenediamine. p-Tolylenediamine CH, CeH,(CH,)(NH,), [1:2:5] te Ane HN Preparation.—By reduction of amidoazotoluene (from o-toluidine) with zine dust and hydrochloric acid (Nietzki, Ber. 10, 1158). Properties. —Colourless tables. Bp. 274°; mp. 64°. Easily soluble in water. Oxidised in presence of aniline or orthotoluidine it gives blue indamines, which on boiling are converted into safranines. m-Phenylene and m-Tolylenediaminesulphonic Acids C.H,(NH,),SO,H [1:3:4] and CgH,(CH,)(NH,),SO3H [1:2:4:5] Obtained by sulphonating m-phenylene- and m-tolylenediamine with fuming sulphuric acid. Small prisms. The first is easily soluble, the latter sparingly soluble in water (Post and Hartung, Ann. 205, 104; Wiesinger, Ber. 7, 464). Diphenyl-m -phenylenediamine C.Hy(NHO,H5). [1:3] Preparation.—By heating resorcin with aniline in presence of calcium chloride and a> little zinc chloride at 210° (Calm, Ber. 16, 2795). Properties—F¥F lat needles. M.p. 95°. Insoluble in water, sparingly soluble in cold alcohol. Di-p-tolyl-m-phenylenediamine GAANHO, Hy [1:5] Prepared in the same way from resorcin and p-toluidine. Long needles. M.p. 137°. (Hatschek and Zega, Jour. Pr. Chem. [2] 33, 218). Diphenyl-(2 : 7)-naphthylenediamine OioHo(NHO;H;) [2:7] de. a Oia Preparation.—By heating (2: 7)- dioxynaphthalene (16 pts.) with aniline (37 pts.) and aniline hydrochloride (13 pts.) at 140° to 180° (Durand and Huguenin, Eng. Pat. 14283°%°; Ger. Pat. 40886°). Properties,—Silvery plates. M.p. 164°. Sparingly soluble in alcohol. | 30° 4 Di-p-tolyl-(2 : 7)-naphthylenediamine CyoH¢(N HC,Hy), [2 : 7] Preparation.—By heating (2:7)-dioxynaphthalene with p-toluidine and p-toluidine hydrochloride (Durand and Huguenin, Joc. cit.). Properties.—Fine needles. M.p. 237°. Nearly insoluble in alcohol. pp-Diamidodiphenylmethane H, [4:1] NH,-CsHy-CH,-CoH,-NH, [1:4] i HNC >—C—¢ NH, Preparation.—(1) By heating formaldehydeanilide C,H, -N:CH, (obtained by passing formaldehyde into aniline) with aniline hydrochloride and aniline at 100° (Meister, Lucius, and Briining, Eng. Pat. 20678; Ger. Pats. 53937” and 55565), (2) From amidobenzyl- aniline, obtained by reduction of p-nitrobenzylaniline, by heating its hydrochloride at 180° to 200° for several hours (Bayer and Co., Ger. Pat. 55848°°). Properties.—Silvery plates (from water) or large crystals (from benzene). M.p. 86°. The sulphate is tolerably soluble in water, sparingly in alcohol. pp-Diamidoditolylmethane [4:1] NH,-C,He- CH, - C,H, NH, [1:4] Preparation.—From formaldehyde and o-toluidine in the same way as the preceding (Meister, Lucius, and Briining). Properties. —Glistening plates. M.p. 149°. Its sulphate is easily soluble. pp-Tetramethyldiamidodiphenylmethane [4:1] (CHs),N - CoH, - CH, - O,H,- N(CH,). [1:4] 3/2 Preparation.—By the action of formaldehyde upon dimethylaniline hydrochloride. Properties._—Glistening plates. M.p. 90°; bp. 390°. pp-Diethyldibenzyldiamidodiphenylmethanedisulphonic Acid CgH,- N(CoH;) - CHe- CsH, - SO3H HLC—C—€_ N(CH) Preparation. —By reduction of tetramethyldiamidobenzophenone OC{O,H, - N(CH,), f. (10 pts.), dissolved in amylalcohol (100 pts.) containing caustic soda (6 pts.) by heating with zine dust (8 pts.) at 120° to 130° for several hours (Bad. Anil. and Soda Fabrik, Eng. Pat. 5645088; Nathansohn and Miiller, Ber. 22, 1879). . Proper Bs —Colourless triclinic prisms. M.p. 96°. Forms colourless solutions in benzene and ether, blue in alcohol and acetic acid. . pp-Diamidodiphenylamine } H HN(O,H,-NH,),{1:4] ie. HNC >-N—< NH, Preparation.—By reducing with zine dust and hydrochloric acid, the bluish violet indamine obtained by oxidation of equal mols. of the hydrochlorides of aniline and p-phenylenediamine in aqueous solution at 0° by means of potassium bichromate (Nietzki, Ber. 16, 474). Properties.—Plates. M.p. 158°. Its sulphate forms thin needles, very sparingly soluble in water. PRIMARY AMINES AND DIAMINES USED IN THE PREPARATION OF SUBSTANTIVE COTTON COLOURS Dehydrothio-p-toluidine (A midobenzenyl-o-amidothiocresol) CHye 0+ OH(NH,)[1 24] ae. Be SoC, Preparation.—Together with primuline base, by heating paratoluidine (2 mols.) with sulphur (4 atoms) at 180° to 250° till the evolution of hydric sulphide has ceased. It is separated from the primuline base by extraction with solvents or by distillation in vacuo (Green, J. Chem. Soc: 1889, 228). Properties—Long yellowish iridescent needles. M.p. 191° uncorr.; b.p. 434° uncorr. at 766 mm. Very slightly soluble in water, moderately in alcohol. Its solutions have a violet-blue fluorescence. Its salts are decomposed by water. When heated with sulphur it yields primuline base 0,H,(CH, <\>0-0H,<\>C-0,H,<\>0-C,H,-NH, with evolution of hydric sulphide. Its diazo compound is easily soluble. Sulphonie acid CyH,(CH,)

C - CpH,(NH,)$0,H. Prepared by sulphonating the base with fuming sulphuric acid at 40° to 50°. It crystallises in yellow needles (+H,O) or orange leaflets (+ 2H,O), insoluble in water. The ammonium salt forms sparingly soluble white plates (+ H,O). The copper salt is a brownish-red insoluble precipitate. Dehydrothioxylidine (Amidotoluenyl-o-amidothioxylenol) HCA. CoH CH; <> C-C,H,(CH,)NH, te. Os aN GH: y Preparation.—By heating metaxylidine (2 mols. or more) with sulphur (4 atoms) at 185° to 190° as long as hydric sulphide is evolved. It is separated from the xylidine-primuline base, which is formed simultaneously, by extracting with solvents or by distillation in vacuo (Anschiitz and Schultz, Ber. 20, 582). Properties. —Y ellowish-white prisms. M.p. 107°; b.p. 283° at 14mm. _ Very soluble in hot alcohol, sparingly in cold, insoluble in water. Its salts are decomposed by water. The diazo compound is easily soluble. By fuming sulphuric acid at 50° it is converted into the sulphonic acid, a sparingly soluble yellow precipitate, whose salts are colourless. Benzidine (Di-p-amidodipheny!) CH, (NH,)[1 24] | : ic. HNC >— NH, C,H,(NH,)[1: 4 ] . 7 Preparation.—Nitrobenzene is reduced with zinc dust and caustic soda in an iron vessel provided with a rapid agitator. After distilling off any aniline which is formed with steam, the product is run out, and the zinc hydrate is removed by treatment with cold dilute hydrochloric acid. The hydrazobenzene C,H,.NH-NH-C,H, which is left insoluble is converted into benzidine by boiling with hydrochloric acid, the solution is filtered, and the benzidine precipitated as filet by the addition of sulphuric acid or sodium sulphate, The base is obtained by decomposing the sulphate with caustic soda, and distilling. For the preparation of cotton azo colours the sulphate is usually diazotised direct, without drying. Properties.—Large colourless silky plates. M.p. 122°; b.p. above 360°. Somewhat soluble in hot water, very slightly in cold. Dilute solutions give dark blue precipitates on the addition of potassium bichromate or potassium ferricyanide. On shaking the solution in carbon disulphide with dilute bromine water the aqueous layer becomes first blue, then green, and finally on adding an excess of bromine water, colourless, whilst the carbon disulphide solution becomes dark red. By nitrous acid it is converted into tetrazodiphenyl C,H,-N:N-OH G.H,-N :N. OH colours, which dye cotton from an alkaline bath without a mordant. By the action of sulphuric acid, ordinary or fuming, under different conditions it is : hehe Pa CeH3(N Hp) converted into the mono- or disulphonic acid or into benzidinesulphone 0.s ( cone 63 2 » which combines with the sulphonic acids of phenols and amines to form azo and its mono- and disulphonic acid (Griess and Duisberg, Ber. 22, 2459). Tolidine (11-p-amidoditolyl) CoH,(CH,)NH, [1 :3: 4] CH, CH; 1.6. itinn: u C,H,(CH;)NH,[1:3: 4] HNC > Ds 2 Preparation.—By reduction of o-nitrotoluene with zinc dust and caustic soda, and conversion of the hydrazotoluene C,H,(CH,) -NH-NH-C,H,(CH,) into tolidine by boiling with hydrochloric acid (see benzidine). Properties.—Glistening plates. M.p. 128°. Sparingly soluble in water, easily in alcohol. Its sulphate is sparingly soluble, though more soluble than benzidine sulphate. o-Methylbenzidine (1i-p-amidophenyltoly!) C,H,- NH,[1:4] CHs ic HNC >—< DEN C,H;(CH,) - NH.[1: 3: 4] Preparation.—(1) By boiling hydrazobenzenetoluene C,H,.-NH-NH-C,H,(CH,) with cone. hydrochloric acid. The hydrazobenzenetoluene is obtained by slowly running nitrobenzene (1 pt.) into a rapidly-stirred mixture of o-toluidine (1 pt.) and powdered caustic soda (1 pt.) heated to 180°, the mixture of azoxy and azobenzenetoluene thus formed being dissolved in boiling alcohol (5 pts.) and reduced with zine dust (1-2 pts.) (Sandmeyer, Eng. Pat. 13767°; Am. Pat. 406669). (2) Together with benzidine and tolidine by reduction of a mixture of nitrobenzene and o-nitrotoluene with zinc dust and caustic soda and treatment of the hydrazo compound with hydrochloric acid (Hirsch, Ger. Pat. 54112"; Ber, 23, 3222). Properties—Plates. M.p. 115°. More soluble in aie than either benzidine or tolidine. The sulphate is very sparingly soluble in water. m-Methylbenzidine (Di-p-amidophenyltolyl) ie. HNC >—— re sHs(OC,Hs)NH[1:3: 4] Preparation.—Benzeneazophenetolsulphonie acid C,H,-N,-C,H,(OC,H,)SO,H [1 : 2 : 5], obtained by combining diazobenzene chloride with phenol-p-sulphonic acid and etherifying the product by heating with ethyl bromide, is reduced in aqueous solution with stannous chloride and hydrochloric acid, or with zinc dust and caustic soda followed by hydrochloric acid. The ethoxybenzidinemonosulphonic acid thus obtained is heated in an autoclave with water at 170° (Cassella and Co., Eng. Pat. 14464°7; Am. Pat. 380067; Weinberg, Ber. 20, 3171). Properties. —Glistening flat needles. M.p. 155°. Sparingly soluble in water, easily in alcohol. The sulphate forms colourless prisms, sontendy soluble in water, easily in hydro- chloric acid, Dianisidine (Di-p-amidodimethouydiphenyl) CsH;(OCH,)NH,[1:3:4] _ ee OCH, HN >— <_ SEM, Preparation.—The methyl ether of o-nitrophenol C,H,(NO,)OCH, is reduced by zine dust and caustic soda to the hydrazo compound C,H (OCH,NH - NHC,H,(OCH,), which is then boiled with hydrochloric acid. C,H,(OCH;)N H, [1 : 3 : 4] Diamidodiphenylene Oxide C,H;- NH, O | 1.6. A on C,H; NH, HNC >—< NH, : Pes. CoH3(SO;H)NH, eg, Penzidutedisulphonse acid, | , obtained by reduction of C,H,(SO;H)NH, nitrobenzene-m- “sulphonic acid in alkaline solution with zinc dust and subsequent treatment with acid, is heated in an autoclave with 407%/ aqueous caustic soda at 230° to 300° (Bayer and Co., Eng. Pats. 7314°° and 7802; Am. Pat, 423569). Properties. — Small white mening M.p. 152°. Its hydrochloride is easily soluble, the sulphate sparingly soluble in water. F Diamidodiphenyleneketoxim ons :N-OH C,H, - NH, eR OH)N :C a SEN = NH, (OH) eee SR Preparation—By the action of hydroxylamine upon diamidodiphenyleneketone OC(C,H,:NH,), (Bad. Anil. and Soda Fabrik, Eng. Pat. 20668*). Pr operties Orange -brown powder. Very slightly soluble in water, soluble in alkalies and acids. Diamidocarbazol C,H: NH, BN i C,H,- NH, Preparation—By nitration of carbazol (10 pts.) in acetic acid solution by nitric acid of sp. gr. 1-38 (13 pts.). The dinitrocarbazol, which is formed, is reduced with zinc dust and caustic soda (Bad. Anil. and Soda Fabrik, Eng. Pat. 14478%; Am. Pat. 401634). Properties.—Silvery plates. M.p. above 250°. Its hydrochloride forms long fine colour- less needles, the sulphate is very sparingly soluble in water. The NH, groups do not appear to be in the para position since it is not identical with the diamidocarbacal obtained by Tauber (Ber. 23, 797) from dinitrobenzidine. p-Diamidostilbene (Diamidodiphenylethylene) [4:1]C,H,(NH,)-CH:CH-C,H,(NH,) [1:4] ie HNC >CH:CHC NH, Preparation—By reduction of dinitrostilbene obtained by adding aqueous caustic soda to a warm alcoholic solution of p-nitrobenzyl chloride C,H,(NO,)CH,Cl (Actienges. f. Anilin- fabrikn., Eng, Pat. 7284:°°). Properties.—Colourless needles or plates. M.p. 227°. Its sulphate and hydrochloride are sparingly soluble. Diamidostilbenedisulphonic Acid [4:2:1]C,H,(NH,)(SO,H) . CH : CH - CsH,(SO,H)(NH,) [1 : 2:4] Preparation.—p-Nitrotoluenesulphonic acid C,H,(CH,)(SO,H)(NO,) [1 : 2:4], obtained by sulphonating p-nitrotoluene with fuming sulphuric acid, is boiled with aqueous caustic soda, and the azoxystilbenedisulphonic acid “ON ethf 80, H} >C,H, which is formed is reduced by adding zine dust and boiling till permanently feos en (Leonhardt and Co., Eng. Pat. 4387%; Am. Pat. 360558; Bea and Schultz, Ber. 19, 3235). Pr operties— Yellowish microscopic needles. Nearly insoluble in water. Its salts are easily soluble. p-Diamidodiphenylurea [1 : 4] C,H,(NH,)NH [1:4]C,H HAONIE)N HO Preparation—By reduction of tetranitrodiphenylurea (Fleischer and Nemes, Ber. 10, 1296). Properties.—Plates. Soluble in hot water, sparingly in cold. asses Diamidoazoxytoluene (Azoxytolwidine) [1 :2:4]CsH,(CH,)(NH,) - N,O - CsHy(NH,)(CH,) [4 :2:1] Preparation.—By alkaline reduction of p-nitro-o-toluidine (Limpricht and Graeff, Ber. 18, 1404), preferably by means of an alkaline solution of sodium stannite (Green and Lawson, J. Chem. Soc. 1891, 1015). Properties.—Yellow needles or orange prisms. M.p.168° uncorr. Insoluble in water. Its salts are moderately soluble in water, sparingly in presence of hydrochloric acid. The hydrochloride forms small colourless needles. Diamidoazotoluene (Azotoluidine) [1 :2:4]C,H,(CH,)(NH,) -N,-CsH,(NH,)(CH,) [42:1] Preparation.—By further reduction of diamidoazoxytoluene in alcoholic solution by means of sodium amalgam (Limpricht and Graeff), or better with sodium stannite (Green and Lawson, J. Chem. Soc. 1891, 1015). Properties —Dark orange prismatic needles. M.p. 203°. Its hydrochloride is soluble in water, but is precipitated by hydrochloric acid. a-Diamidonaphthalene (Naphthylenediamine) NH, CyoH (NH), 2. Nu, Preparation.—(1) By reduction of a-dinitronaphthalene of m.p. 216° (Zinin, Ann. 52, - 361; 85,329; Aguar, Ber. 7, 306). (2) By heating (1:5) dioxynaphthalene with aqueous ammonia at 150° to 300° (Ewer and Pick, Amn. 247, 361). Properties.—Colourless prisms. M.p. 190°. Soluble in hot water, nearly insoluble in cold. Sublimes. Ferric chloride gives a bluish-violet precipitate. The sulphate is almost insoluble in dilute sulphuric acid. Diamidonaphthalenedisulphonic Acid NH, 2 _-HO,S C,)H4(N H,).(S03H). {1 > 5200 7] v.€. SO,H Ni, Preparation —By dinitration and reduction of (2:6)-naphthalenedisulphonic acid (Cassella and Co., Eng. Pat. 15346). Properties—The acid is nearly insoluble in water. The sodium salt dissolves in 21 pts. of water at 15° It gives a sparingly soluble light yellow tetrazo-compound. It combines with diazo compounds. Diamidonaphthalenedisulphonic Acid NH, NH, C,H,(NH,),(SOH)9[1:8:3:6] ae. ete ee HO,S S0,H Preparation—By dinitration and reduction of (2:7)-naphthalenedisulphonic acid (Cassella and Co., Eng. Pat. 15346"). Properties—Long thin needles; easily soluble in hot water. Its sodium salt forms long pointed needles, soluble in 55 pts. of water at 15°. It does not yield a tetrazo compound but combines with diazo compounds. Heating with dilute sulphuric acid at 120° converts it into amidonaphtholdisulphonic acid (“acid H”). PHENOLS AND THEIR SULPHONIC AND CARBOXYLIC “ACIDS o- and p-Phenolsulphonic Acids C,H ,(OH)SO,H OH OH SO,H 1.€. and Preparation—The two isomers are formed by the action of cone. sulphuric acid upon phenol (equal mols.). At ordinary temperatures the o-sulphonic acid is chiefly formed; at 100° to 110° the product is almost exclusively the p-sulphonic acid. Properties—The para acid forms a syrup. ‘The salts of the ortho acid are more soluble than those of the para. S0,H Salicylic Acid (Phenol-o-carboxylic Acid or o-Oxybenzoice Acid) OH CO,H C.H,(OH)CO,H i.e. O Preparation—Dry sodium phenol (from phenol and caustic soda) is submitted to the action of dry carbonic acid at the ordinary temperature as long as the gas is absorbed. The product, which is sodium phenyl carbonate C,H,-O-CO,Na, is heated in a closed vessel at 120° to 130° for several hours, when it undergoes isomeric change and is converted quantitatively into sodium salicylate. The latter is dissolved in water, and the salicylic acid is precipi- tated by the addition of a mineral acid (Schmitt, Eng. Pat. 10167%4; Am. Pat. 334290). : Properties—Fine white needles. M.p. 156°. Is volatile with steam. Sparingly sol- uble in cold water (1 pt. in 1800 pts.), easily in hot water. Ferric chloride gives a violet coloration. Its salts are easily soluble. It combines with diazo compounds. Valuation—It should dissolve in pure sulphuric acid to a colourless solution (not yellow). It should melt correctly and leave no residue on ignition. Higher homologues are detected and estimated by titration with standard caustic soda or baryta, or by distillation with lime and examination of the phenol obtained (Ewell and Prescott, Analyst, 18, 208, 237). Cresotic Acids (Cresolcarboxylic Acids or Oxytoluic Acids) C,H,(CH,)(OH)CO,H The homologues of salicylic acid are obtained by the action of carbonic acid upon 0- m- or p-cresol in the same way as in the preparation of salicylic acid. o-Cresotic acid (1: 2:3): long flat needles of m.p. 164°. m-Cresotic acid (1:3:4): needles or monoclinic pillars of m.p. 177° corr. p-Cresotic acid (1:4:5): very long needles of mp. 151°. They are all sparingly soluble in cold water, volatile with steam, and give a violet colour with ferrie chloride (Engelhardt and Latschinow, Zezt. f, Chem. 1869, 622), Resorcinol (i-Dioxybenzene) OH C.H,(OH).[1:3] ae. Gls Preparation.—Benzene is converted into the disulphonic acid C,H,(SO,H), by heating it with fuming sulphuric acid or with cone. sulphuric and sodium sulphate. The product is limed and converted into the sodium salt, and the latter is fused with twice its weight of ee al caustic soda at 270° for several hours. The melt is dissolved in water, neutralised with hydrochloric acid, and the resorcin extracted by shaking the liquor with amyl alcohol. The erude resorcin left after distilling off the amy] alcohol is purified by crystallisation from benzene or by distillation in vacuo (Miihlhauser, Ding. Pol. J. 268,154; J. Soc. Chem. Ind. 1887, 284). Propertves.—Colourless rhombic crystals. M.p. 118°; bp. 277°. Very soluble in water and alcohol, insoluble in chloroform and carbon disulphide. Sweet taste. Gives a dark violet colour with ferric chloride. Heated with dibasic acids, such as phthalic, succinic or tartaric acid, it gives yellow colours with brilliant green fluorescence. Lstimation—By treatment with standard bromine water, and titration of the excess of bromine with potassium iodide and sodium thiosulphate. Valuation—The commercial product is usually nearly chemically pure. It should be light in colour, dissolve completely in ether, and have nearly the correct melting point. Water is estimated by drying over sulphuric acid. Orcinol (m-Dioxytoluene) C H3(CHs)(OH), [1:3 : 5] Preparation. By caustic soda fusion from the (1:3: 5)-toluenedisulphonic, obtained by eliminating NH, from the disulphonic acids of ortho- or paratoluidine by heating the diazo compounds with alcohol (Nevile and Winther, Ber. 15, 2987; Eng. Pat. 4389*). Properties—Monoclinic prisms (+H,O). Very soluble in water. M.p. 108°; bp. 290°. On heating its alkaline solution with chloroform a bright red colour is formed which on dilution shows an intense green fluorescence. It is oxidised by air in presence of ammonia to orcein. Pyrogallol ( Pyrogallic Acid or ¢-Triouybenzene) OH C.H,(OH),[1:2:3] we. O OH Preparation—1) By heating gallic acid with 5 times its weight of water in an auto- clave at 200° to 210° (De Luynes and Esperandieu, Ann. (1866) 188,60). (2) By heating gallic acid dissolved in 3 times its weight of glycerine in an open vessel at 190° to 200° as long as carbonic acid is evolved (Thorpe, Ber. 14, 1001). The yield by either method is theoretical. Properties.—White needles or thin plates. M.p. 132° uncorr.; bp. 210. LHasily soluble in water (1 in 24 at 13°). Its alkaline solution rapidly absorbs oxygen from the air and becomes dark in colour. Gallic Acid (7rioxybenzoie Acid) OH OH C,He(O).CO.H fl 32:33. 15 10 vie: HO,CL JOH Preparation—Finely powdered gall-nuts (preferably Chinese galls) are moistened with water and allowed to ferment in a warm place with addition of some beer yeast. The product is extracted with boiling water and filtered, the gallic acid crystallising from the filtrate on cooling. Properties,—Silky needles (+ H,O). Melts with decomposition at 220° to 240°. 1 pt. dissolves in 130 pts. of cold water, in 3 pts. of boiling water. Ferric chloride gives a blue- black coloration. It is not precipitated by solutions of gelatine (distinction from tannic acid). Eee a a-Naphthol (a-Oxynaphthalene) OH C,)H, > OH 1.e OO Preparation.—By fusing sodium a-naphthalene sulphonate (1 pt.) with caustic soda (2 or 3 pts.) and a little water at 270° to 300° in an iron pot provided with a mechanical stirrer. The sodium naphtholate which rises to the surface is separated from the lower layer of caustic soda and sodium sulphite, dissolved in water, and decomposed with hydro- chloric or better with carbonic acid. The precipitated naphthol is dried and distilled. Properties.—Colourless glistening needles. M.p. 94°; bp. 280°. Slightly soluble in hot water, nearly insoluble in cold. Volatile with steam. Dissolves readily in caustic alkales. With chloride of lime it gives a dark violet colour. Valuation—The commercial product forms white crystalline lumps. It usually contains 5 or 10% of S-naphthol, which can be estimated approximately by taking the melting point and comparing with that of standard mixtures of pure a- and B-naphthol. It should dissolve in caustic soda with very little residue. a-Naphtholearboxylic Acid (a-Oxy-B-naphtholic Acid) | C,)H¢(OH)CO,H [1 : 2] Preparation.—From sodium a-naphtholate and carbonic acid in the same way as salicylic acid (Schmitt and Burkard, Ber. 20, 2699; Ger. Pat. 31240; Am. Pat. 350468), Properties—Needles. M.p. 186°. Sparingly soluble in water. Its salts are sparingly soluble. Blue coloration with ferric chloride. a-Naphtholmonosulphonic Acids C,)H,(OH)SO,H Of the various isomeric sulphonic acids of a-naphthol the (1:4)-acid is by far the most important, the others at present finding only a limited employment. a-Naphtholsulphonic Preparation—(1) By boiling diazotised naphthionic acid with acid NW. (1: 4) dilute sulphuric acid (Nevile and Winther, Ber, 13,1949). (2) (Nevile and Winther’s acid) By heating sodium naphthionate (1 pt.) with 507% aqueous caustic soda (1 pt.) im an autoclave for 10 hours at 240° to 260° (Actienges. f. Anilinfabrikn., Ger. Pat. 46307), Properties—Very soluble transparent tables. Mp. 170°. SO;H Ferric chloride gives a blue coloration, becoming red on heating. (Constituiion: Witt and Nitrous acid gives a yellow crystalline nitroso compound. With Kaufmann, Ber, 24, 3157) nitric acid it yields dinitronaphthol. Its salts are very soluble. OH a-Naphtholsulphonic Preparatwn.—(1) By adding strongly fuming sulphuric acid acid (1:2) to a-naphthol dissolved in twice its weight of glacial acetic (Scheeffer's or Bawm’s acid) acid (Baum, Eng. Pat. 3498%). (2) By heating a-naphthol OH (1 pt.) with cone. sulphuric acid (1 pt.) for $ hour at 90°, SO,H dissolving in water (5 pts.), and neutralising with soda: on OO cooling the sodium salt crystallises out in silky plates. Properties.—Long soluble needles. M.p. 101°. Ferric chloride gives a blue colour, becoming green on heating. By nitric acid it is converted into dinitronaphthol. The sodium salt is tolerably soluble, the barium salt sparingly soluble. [ 39 ] a-Naphtholsulphonic Preparation —(1) By caustic soda fusion of naphthalenedi- acid (1:3) sulphonic acid (1:3) obtained by eliminating the NH, group (Armstrong and Wynne’s acid) from ®B-naphthylaminedisulphonic acid G (Armstrong and On Wynne, Proc. Chem. Soc. 1890, 13; Bad. Anil. and Soda Fabrik, OO Eng. Pat. 9537%), (2) By heating a-naphthylaminedisulphonic SO,H acid e with water or dilute acids at 150° to 250° in an autoclave (Kalle and Co., Ger. Pat. 64979%), a-Naphtholsulphonic Preparation.—(1) By boiling the diazo compound of Laurent’s acid L, (1:5) a-naphthylaminesulphonic acid with dilute sulphuric acid (Cleve’s acid) (Cleve, Bl, 24, 512). (2) By fusing naphthalenedisulphonic OH acid (1:5) with caustic soda at 160° to 190° (Ewer and Pick, Ger. Pat. 41934°), Properties. — Deliquescent crystalline solid. The sodium 50H salt forms transparent prismatic needles. a Naphtholsulphonic Preparation.—By heating naphthalenedisulphonic acid acid (1:6) (1:6) with aqueous caustic soda under pressure. Also by OH decomposition of the diazo compound of Cleve’s a-naphthyl- ai CL) amine-8-sulphonic acid by boiling with dilute sulphuric acid. 3 a-Naphtholsulphonic Preparation.—By sulphonating a-naphthol (1 pt.) with cone. acid (1:7?) sulphuric acid (4 pts.) and boiling the barium salt of the (Liebiann and Studer’s acid) disulphonic acid with cone, hydrochloric acid for 2 hours. OH Properties.—It gives a crystalline nitroso compound, which HO,S is converted by nitric acid into dinitronaphtholsulphonic acid ee (“ Naphthol yellow $8”). a-Naphtholsulphonic Preparation.—By boiling the diazo compound of a-naphthyl- acid 6 or Sch. (1:8) aminesulphonie acid Sch. with dilute sulphuric acid, and heating (Schollkopf acid) the sultone with aqueous alcohol (Schollkopf Anil. Co., Eng. Pat. SO,H OH 15775"; Am. Pat. 333034; Erdmann, Ann. 247, 343). Properties—Very soluble crystalline solid. M.p. 107°. Ferric chloride gives a dark green colour, becoming first yellow and then red. On dehydration it is converted into the sultone Cul which crystallises in prisms of mp. 154° and b.p. above 360°, and is insoluble in water (Schultz, Ber. 20, 3162). By nitric acid it is converted into a dinitronaphthol- sulphonic (“ Brilliant yellow ”). a-Naphtholdisulphonic Acids C,)H;(OH)(SO;H), The following isomers have more or less technical importance :— a-Naphtholdisulphonic Preparation.—By sulphonating a-naphthol (1 pt.) with cone. aciae(l ; 2:4) sulphuric acid (3 pts.) for a short time at about 70°. OH Propertics—By nitric acid it is converted into dinitronaphthol (Martius yellow). It does not combine with diazo compounds or form a nitroso compound. S03H SO,H a-Naphtholdisulphonic acid (1:2:7)@ OH ae yeaa a-Naphtholdisulphonic acid 6 or Sch. (1: 4:8) S03;H OH SO,H a-Naphtholdisulphonic acid « (1:3: 8) SO,H OH SO,H a-Naphthol- disulphonic acids (1:4:6) and (1:4: 7) (Dahl’s acids) OH OH HO.S ll and SO,H S0,H Pea Preparation. By heating a-naphthol (1 pt.) with cone. sulphuric acid (2 to 3 pts.) for two hours at 125° to 130° (Leonhardt and Co., Eng. Pat. 11318*; Bender, Ber. 22, 996). Properties—It forms a nitroso compound which is converted by nitric acid into dinitronaphtholsulphonic acid (“ Naphthol yellow 8S”). By boiling the diazo compound of water. (2) By sulphonating naphthosultone Gene with 3 pts. of cone. sulphuric acid at 100° (Schéllkopf Anil. Co., Eng. Pats. 15775® and 15782; Bernthsen, Ber. 28, 3090). Properties—The sodium salt forms very soluble plates ; the barium salt is sparingly soluble. Ferric chloride gives a blue coloration. It combines with diazo compounds. On dehydration it yields the sultonesulphonic acid OypHi($0) <9? The sodium salt of the latter is sparingly soluble and its barium salt easily soluble. Preparation.—(1) a-naphthylaminedisulphonic acid 6 with Preparation.—By boiling the diazo compound of a-naphthyl- aminedisulphonice acid with dilute sulphuric acid; on cooling the sultonesulphonic acid ecrystallises out and is converted into salts of the disulphonic acid by dissolving in alkalies (Actienges. f. Anilinfabrikn., Eng. Pats. 4625°° and 5910%§ ; Ewer and Pick, Ger. Pat. 52724°). Properties.—The sodium salt forms very soluble long colourless prisms (+6H,O). Ferric chloride gives a deep blue colour. Sultonesulphonic acid (€ acid) C,yH,(S0,H)<,, ?—Formed by dehydration of the disulphonic acid. Silky needles. M.p. 241°. Easily soluble in water. Converted by ammonia into the amide acid C,,H,(SO,H)(SO,NH,)OH. The sodium salt forms long colourless needles (+ 3H,O), sparingly soluble in cold water. No coloration with ferric chloride (Bernthsen, Ber, 22, 3330). Preparation.—Obtained from Dahl’s a-naphthylaminedi- sulphonic acids II. and III. respectively, by boiling the diazo compounds with water (Dahl and Co. Ger. Pat. 419575), Propertus. — By nitric acid they are converted into dinitronaphtholsulphonic acids, that from the latter being identical with “ Naphthol yellow S” (Armstrong and Wynne, Proc. Chem, Soc. 1890, 17). The following two acids a-Naphtholtrisulphonic acid (1:2:4:7) OH HO, SO,H SO,H a-Naphtholtrisulphonic acid (1:3:6:8) HO;S OH HO2$ SO,H a-Naphtholtrisulphonic acid (1:2:4:8) HO.S OH SO,H SO,H [.41 ] a-Naphtholtrisulphonic Acids C,)H4(OH)(SO;H)s are of technical importance :— Preparation—bBy the action of fuming sulphuric acid of 50% SO, (4 pts.) upon a-naphthol (1 pt.) at 40° to 50° for 6 hours (Bad. Anil. and Soda Fabrik, Eng. Pat. 53057), Propertves.—It does not combine with diazo compounds or form a nitroso compound. By nitric acid it is converted into dinitronaphtholsulphonic acid (“ Naphthol yellow 8 ”). Preparation.—From. the corresponding a-naphthylamine- sulphonic acid (¢.v.) by boiling its diazo compound with water (Koch, Eng. Pat. 9258). Propertves—By dehydration it yields a naphthosultonedi- sulphonic acid. Preparation— By further sulphonation of napthosultone, or of a-naphtholmono- or di-sulphonic acid Sch. with fuming sulphuric acid of 25'% SO, (Bayer and Co., Eng. Pat. 3397), Properties.—Does not combine with diazo compounds. Converted by nitric acid into a dinitronaphtholsulphonic acid. 8-Naphthol (8-Oxynaphthalene) C,H * OH 1.€. POs ue Preparation—By fusing sodium #-naphthalene sulphonate (1 pt.) with caustic soda (2 pts.) in the same way as a-naphthol (¢.~). Properties—Colourless plates or rhombic tables. M.p. 125°; bp. 286°. Sparingly soluble in water, easily in alcohol, ether, etc. Not volatile with steam. LDissolves readily in caustic alkalies. Like a-naphthol it gives a transient blue coloration on warming its alkaline solution with chloroform. Ferric chloride or chloride of lime gives no coloration. Valuation—The commercial product is nearly chemically pure. It forms yellowish- white crystalline lumps which have very little odour. It should have nearly the right melting point (120° to 121° C.) and dissolve in caustic soda to a colourless solution, leaving very little residue. The presence of a-naphthol is detected by dissolving in alcohol, diluting with water and adding a few drops of ferric chloride; the formation of a violet-blue colour indicates the presence of a-naphthol (usually -1'/ to -5%). 8-Naphtholmonosulphonic Acids C,)H,(OH)SO3H The following four isomers are employed for the preparation of colours either separately or more or less mixed with one another. 8-Naphtholsulphonic acid Preparation.—Together with the @-acid by dissolving finely a or B, (2:8) powdered §-naphthol (1 pt.) in cone, sulphuric acid (2 pts.) at (Bayer’s acid) 50° to 60° (Bayer and Co. Eng, Pat. 1225%! and 2030%; SO0.H Am Pat. 256381); or by the action of conc. sulphuric acid in the cold upon $-naphthol for several days (Leonhardt and Co., Ger. Pat. 33857%*), The a-acid is separated from the G Gk §8-Naphtholsulphonic acid B or §, (2:6) (Schaffer’s acid) OH HO,S 8-Naphtholsulphonic acid y or D, (2:5) (Dahl's acid) OH HO;S 8-Naphtholsulphonic acid re) oe py Oa (Cassella’s acid) HO. ) OH [ 4Be B-acid, which is formed simultaneously, by precipitating the latter as sodium salt by adding sodium chloride; or more com- pletely by adding to the alkaline solution the requisite quantity of a diazo chloride, which combines first with the A-acid. Properties.—Its sodium salt C,,H (ONa)SO,Na is very sol- uble in water, easily in hot 90% alcohol. Preparation—By heating $-naphthol (1 pt.) with cone. sulphuric acid (1 to 2 pts.) at 100°; on dissolving the melt in water and adding salt, the sodium salt of the #-acid cerystallises out whilst isomeric acids formed simultaneously remain in solution (Schiffer, Ann. 152, 296; Armstrong and Graham, J. Chem. Soc. 39, 136; Eng. Pat. 7098*). Properties—Very soluble small colourless plates. M.p. 125°. The sodium salt forms long colourless needles or plates (+ 2H,O), moderately soluble in water, insoluble in alcohol. Nitrous acid forms nitrosonaphtholsulphonic acid, the iron salts of which are deep green colouring matters. Preparation.—From the f-naphthylamine-y-sulphoniec acid by boiling its diazo compound with water (Dahl and Co., Eng. Pats. 7712 and 7713; Forsling, Ber. 20, 2099). Preparation.—By fusing naphthalenedisulphonie acid (2 : 7) with caustic soda at 200° to 250°, or by heating it in an auto- clave with aqueous caustic soda (Cassella and Co., Ger. Pat. 42112°°; Eng. Pat. 12908%°; Weinberg, Ber. 20, 2906). Properties—Needles. M.p. 89°. Very soluble in water and alcohol. ferric chloride gives a dark blue coloration. The sodium salt is easily soluble, the barium salt sparingly soluble. 8-Naphtholdisulphonic Acids CioH;(OH)(SO;H), The following are of technical importance :— 8-Naphtholdisulphonic acid Preparation—By heating S-naphthol (1 pt.) with cone. a or R, (2:3:6) OH HO,S\A/803H (Constitution : Armstrong and Wynne, Proc. Chem. Soc. 1890, 12) sulphuric acid (3 pts.) at 100° to 110° for several hours. On dissolving the melt in water, and adding salt, the nearly pure sodium salt of the R-acid (“ R-salt”) erystallises out, whilst the “G-salt,’ which is formed simultaneously, remains in solution (Meister, Lucius, and Briining, Eng. Pat. 1715"; Griess, Ber. 13, 1956; Beyer and Kegel, Eng. Pat. 7097*). Properties.—Deliquescent silky needles. Very soluble in water. The alkaline solution has a bluish-green fluorescence. Its sodium salt is insoluble in alcohol. It combines with diazo compounds much more readily than the G-acid. B-Naphtholdisulphonic acid Preparation.—By dissolving 8-naphthol (1 pt.) in cone, sul- B vy, or G. (2:6: 8) phuric acid (4 pts.), and keeping at 60° for 48 hours, or at 20° 0.8 for 8 to 10 days. The product consists mainly of the G-acid, OH together with 10% to 15% of the monosulphonic acid §, which HOS latter is removed by treating the alkaline solution with the (Constitution: Armstrong necessary quantity of diazobenzene chloride to combine with it, and Wynne, Proc. Chem. and filtering from the orange produced (Meister, Lucius, and Soc. 1890, 12) Briining, Eng. Pat. 816**; Am. Pat. 331059), Propertves—Its sodium salt forms colourless plates or prisms, soluble in 90% alcohol. The salts are more soluble in water than those of the R-acid. B-N aphtholdisulphonic acid Preparation—By heating B-naphtholmonosulphoniec acid 6 Combate 23 : 7) with cone. sulphuric acid (2 pts.) at 120° for 12 hours (Cassella and Co., Ger. Pat. 440708; Eng. Pat. 826598; Hos(( ox Weinberg, Ber. 20, 2912). SO,H _Properties.—Its salts have a green fluorescence, the barium (Constitution: Armstrong salt forms small prisms (+ 23H,O), sparingly soluble in boil- and Wynne, Proc. Chem. ing water. The sodium salt is easily soluble in water, spar- Soc. 1890, 127) ingly in alcohol. 8-Naphtholdisulphonic Preparation.—From the corresponding §-naphthylamine- acid C. (2:4:8) disulphonic acid C by boiling the diazo compound with water HO0,8 (Cassella and Co., Ger. Pat. appl. C. 3542). OH Properties. —Its alkaline solution has a_ pure blue fluorescence. SO,H 8-Naphtholtrisulphonic Acid CjpH,(OH)(SO3H); Probably (2:3:6:8) Preparation.—By heating 8-naphthol (1 pt.) with fuming HO,S sulphuric acid of 207% SO, (4 to 5 pts.) at 140° to 160°, or by OH heating 8-naphthol with a large excess of sulphuric acid HO,¢ OR for a long time (R. Meldola, Eng. Pat. 1864; Meister, Lucius, and Briining, Eng. Pat. 2544*; Levinstein, Ber. 16, 726). The first product of the reaction appears to be the sultonedi- sulphonic acid CiH (SOB).

CH,Cl Preparation.—By leading chlorine on to the surface of boiling toluene until it has in- creased in weight by 387%. The product is washed with water and separated by fractional distillation from unaltered toluene and from benzylidene dichloride and _ benzotrichloride, which are formed simultaneously. Properties. —Colourless liquid. B.p. 178°; sp. gr. at 14°=1-107. Insoluble in water. Pungent smell. Valuation.—The commercial product is far from pure: it contains toluene, benzylidene chloride, benzotrichloride, and sometimes chlorotoluenes. It usually boils between 175° and 182°. Its value in benzotrichloride may be estimated by observing the amount of green colouring matter produced on heating with dimethylaniline and zine chloride. The quantity of chlorine present as evxo-chloro substitution products is estimated by boiling a weighed sample with alcoholic silver nitrate and weighing the silver chloride produced; chlorine present in the nucleus is not eliminated by this treatment (Schulze, Ber. 17, 1675). Benzylidene Dichloride (Benzal Chloride) and Benzotrichloride C,H,-CHCl, and 0,H,-CCl, Preparation.—Are formed together by the further chlorination of boiling toluene. They are usually not separated but are employed at once for the preparation of benzaldehyde and benzoic acid by heating the mixture with milk of lime. Properties.—Colourless oily liquids. Benzylidene dichloride has the sp. gr. at 15° = 1-25, and boils at 206°. Benzotrichloride has the sp. gr. at 14° = 1-38, and boils at 214°. On saponification benzylidene dichloride gives benzaldehyde, benzotrichloride gives benzoic acid. p-Nitrobenzyl Chloride CgH,(NO,) - CH, Cl [1 : 4] Preparation.—By passing chlorine into p-nitrotoluene heated to 185° to 190° (Wachendorff, Ann. 185, 271); or by dropping benzyl chloride into fuming nitric acid cooled to —15° (Strakosch, Ber. 6, 1056), Properties.—Plates or needles. M.p. 71°. ALDEHYDES, KETONES, AND QUINONES Benzaldehyde (Ditier-almond Oil) C.H;-CHO ie < CHO Preparation—(1) By heating the mixture of benzylidene dichloride and benzotrichloride, obtained by chlorinating toluene, with the calculated quantity of milk of lime under a pressure of 4 to 5 atmospheres. The benzaldehyde is distilled off with steam whilst calcium benzoate, which is formed simultaneously, remains behind. (2) By heating the mixture of benzyl chloride (2 mols.) and benzylidene dichloride (1 mol.), obtained by chlorinating toluene until the sp. gr. of the liquid is 1-175, with finely powdered manganese dioxide (2 mols.) suspended in water (Schmidt, Ger, Pat. 20909%). The former method is generally employed. H gr. of bitter almonds. Bp. 180°. Sp. 412=1-0504. Slightly soluble in water, miscible with alcohol. Valuation.—The commercial product, which is tolerably pure, should distil to the extent of 90°/ between 177° and 181°, and should have the correct specific gravity. It should dissolve almost completely in 10 times its volume of warm aqueous sodium bisulphite of sp. gr. 1-11; on extracting this -solution with a little ether and evaporating off the ether, there should be no pungent smelling residue left (benzyl chloride, etc.). The presence of chlorine is detected by the copper oxide microcosmic bead, or by fusion with sodium hydrate and nitrate and precipitation with silver nitrate. When it has been kept for some time it contains benzoic acid, which crystallises out. Adulteration with nitrobenzene is detected by the production of a green colour on heating with strong aqueous potash, and by the presence of nitrogen (formation of cyanide on ignition with sodium). m-Chlorobenzaldehyde Cl CsH,Cl- CHO[1:3] ae. < CHO Preparation.—By chlorination of benzaldehyde in presence of zinc chloride (Miiller, Ger. Pat. 330648%) ; or better from m-amidobenzaldehyde by diazotisation and treatment with cuprous chloride (Meister, Lucius, and Briining). Properties—Oil. Bp. 210° to 213°; sp. gr. 1-246. Dichlorobenzaldehyde C,H,Cl,- CHOI :2: 4] Preparation. — From the dichlorobenzylidene cick eee C,H,Cl, - CHCl, obtained by chlorination of (1:3: 4)-dichlorotoluene at 150° to 170°, by heating it with 100 Ps sulphuric acid at 40° to 50° (Bad. Anil. and Soda Fabrik, Ger. Pat. 32238%4). Properties —Crystalline solid. M.p. 58°; b.p. 234°. On nitration it is converted into a dichloro-o-nitrobenzaldehyde, which forms eel plates of m.p. 138° and gives tetrachlor- indigo on heating with acetone and aqueous soda. o-N itrobenzaldehyde | NO CyH,(NO,)CHO[1:2] te < >CHO Preparation.—F rom o-nitrobenzyl chloride by conversion into the acetate, benzoate, sulphite, etc., and oxidation with nitric acid (Fischer, Ger. Pat. 487225). Properties—Long yellow needles. M.p. 46°. Gives indigo on treatment with acetone and aqueous soda. m-Nitrobenzaldehyde NO, C.Hs(NO,)CHO[I :3]' ie. < CHO Preparation.—By slowly adding benzaldehyde (10 pts.) to potassium nitrate. (11 pts.) dissolved in cone. sulphuric acid, iene the temperature below 10° Ee and Henriques, Ber, 14, 2802; Ehrlich, Ber. 15, 2010). . | Properties.—Y ellow needles. M.p. 58°. p-Nitrobenzaldehyde CgH,(NO,)CHO[1 :4] te. ONC CHO Preparation—By boiling p-nitrobenzyl chloride (1 pt.) with a solution of lead nitrate (5 pts.) in water (10 pts.) for 24 hours, or for 12 hours with a saturated solution of cupric nitrate. The yield is nearly theoretical (Faust, Mon. Scien. 1885, 1262). Properties.—Long thin prisms. M.p. 106°. Tolerably soluble in hot water, slightly in cold. m-Amidobenzaldehyde NH, CsH,(NH2)CHOf1:: 3] ze. < CHO Preparation—By reduction of the sodium bisulphite compound of m-nitrobenzaldehyde with ferrous hydrate (Meister, Lucius, and Briining, Eng. Pat. 11049; Ger. Pat. 62950), Properties—tThe free base cannot be isolated, as when liberated from its salts it at once passes over into its anhydride C_H,N, a crystalline body of high melting point and sparing solubility. p-Dimethylamidobenzaldehyde OgH,{ N(CH,),}CHO[1:4] te. (CH;).N< CHO Preparation—A mixture of dimethylaniline (12 pts.), anhydrous chloral (14 pts.), and phenol (9 pts.) is allowed to stand at the ordinary temperature for several days. The phenol is then removed by shaking with dilute caustic soda, and the crystalline residue is dissolved in boiling water and hydrochloric acid. On cooling the sparingly soluble hydrochloride of the base C,H, {N(CH,), }-CH(OH)-CCl, crystallises out, which is converted into p-dimethyl- amidobenzaldehyde and chloroform by heating with the theoretical quantity of alcoholic caustic soda (Bossneck, Ber. 18, 1516; 19, 365; Zierold, Ger. Pat. 61551%). Propertves—Colourless plates. M.p. 73°. Soluble in hot water. p-Diethylamidobenzaldehyde CsHa{ N(C,H,), | CHO[L : 4] Obtained from diethylaniline and chloral in the same way .as the preceding. It forms colourless needles of m.p. 41°, soluble in water. o- and p-Oxybenzaldehyde O,H,(OH)CHO[1:2] and [1:4] Preparation.—These two isomers are obtained together by boiling phenol (1 pt.), aqueous caustic soda of 20°/ NaOH (15 pts.), and chloroform (2 pts.). The acidified pro- duct is distilled with steam, when o-oxybenzaldehyde and unaltered phenol and chloroform distil over and are separated by sodium bisulphite, whilst p-oxybenzaldehyde remains behind and crystallises from the residue on cooling (Tiemann and Reimer, Ber. 9, 824; 10, 63, 213). _ Properties—The o-compound is a pleasant-smelling liquid of b.p. 196° and sp. gr. at 14°=1:173. The py-compound forms colourless needles of mp. 116°. They are both soluble in hot water, and combine with alkaline bisulphites. [ 52 ] m-Oxybenzaldehyde C.H,(OH)CHO[I : 3] Preparation.—From m-amidobenzaldehyde by heating its diazo compound with water (Tiemann, Ber. 15, 2045), Properties.—Colourless needles. M.p. 104°; b.p. 240°. Soluble in hot water. Methyl ether C,H(OCH,)CHO. Liquid of b.p. 230°, nearly insoluble in water. p-Dimethylamidobenzophenone ; O C,H; - CO - C,H,N(CH,), [1:4] ie. < >-C—<_N(CH,)s Preparation. Benzanilide C,H,- CO: NH - C,H, (2 pts.) is heated with dimethylaniline 4 pts.) and phosphorous oxychloride (2 pts.) for 2 or 3 hours at 100° to 120°. The pro- duct is made alkaline and freed from excess of dimethylaniline by distillation with steam. The solid residue C,H,- C(NC,H,) - C,H,- N(CH,), is filtered off and heated with hydrochloric acid (1 pt.) and water (10 pts.) at 50° to 70°, by which it is decomposed into aniline and dimethylamidobenzophenone, which latter separates as a crystalline precipitate from the deep yellow solution which is first formed (Meister, Lucius,-and Briining, Eng. Pat. 52578"). Properties,— White needles. Mp. 70°. Easily soluble in alcohol. Weak base. pp-Tetramethyldiamidobenzophenone O [4:1}(CH,),N - CsH,- CO -C,H,- N(CH), [1:4] ire. (CH;).NK S—C—C_>N(CHs)s Preparation.—Carbonyl chloride is passed into dimethylaniline at the ordinary temper- ature until the latter has increased in weight by 407. The product, which chiefly consists of dimethylamidobenzoyl chloride and dimethylaniline, is then heated for several hours at 100° to complete the reaction (Michler, Ber. 9, 715, 1900). , Properties.—Colourless plates. M.p. 174° corr. Easily soluble in alcohol, insoluble in water. Chloride {(CH,),N - C,H,},CCl,—Obtained by the action of phosphorus chlorides or oxychloride upon the ketone. pp-Tetraethyldiamidobenzophenone [4:1](C,H5).N - CgH,- CO - CgHy- N(CH). [1 : 4] Obtained from diethylaniline and carbonyl chloride in the same way as the preceding. Small yellowish plates. M.p. 96°. pp-Tetramethyldiamidothiobenzophenone [4 :1](CH,),N - C,H, - OS - CsH, -N(CHs), [1: 4] Preparation—By slowly adding thiocarbonyl chloride (10 pts.) diluted with carbon disulphide (30 pts.) to dimethylaniline (50 pts.), keeping the temperature at 0° to 10° by external cooling. After agitating for 10 or 12 hours, the mixture is made alkaline, the carbon disulphide and excess of dimethylaniline is distilled off with steam, and the thio- ~ ketone remains behind (Kern, Eng. Pat. 12022%; Baither, Ber. 20, 1732, 3290). Properties.—Ruby-red plates with steel-blue reflex. M.p. 202°. On heating with dilute hydrochloric acid it is decomposed into tetramethyldiamidobenzophenone and hydric sulphide. . [ 53 ] Anthraquinone OF 9. CO : ) fp eam [2:1]C.Hy<66 > CoH, [1:2] te, ie ; O v Preparation.—By oxidation of anthracene with chromic acid, the operation being per- formed in the following manner: Finely powdered commercial anthracene, containing 60 to 807% pure anthracene, is stirred up with a boiling solution of sodium or potassium bichromate (1 mol. of bichromate to every mol. of true anthracene present). A dilute solu- tion of sulphuric acid (containing 4 mols. of sulphuric acid to every mol. of bichromate used) is then very slowly run in, the operation occupying 9 or 10 hours; the mixture is finally boiled for some time to complete the oxidation, and the crude anthraquinone is filtered off, dried, and ground. The product, which also contains the phenanthrene, carbazole, acridine, etc., present in the crude anthracene, is purified by heating it with 2 or 3 times its weight of cone. sulphuric acid at 110° for some time, and then pouring into water. By this treat- ment the impurities are converted into soluble compounds (sulphonic acids, etc.), which remain in solution whilst the anthraquinone is unattacked and precipitates as a nearly white erystalline powder. After washing with soda it is filtered off and dried. It contains 90 to 95% of pure anthraquinone, and is employed at once for the preparation of alizarin. By sublimation it can be obtained quite pure (Kopp, Mon. Scien. [3] 8, 1159; Graebe and Liebermann, Mon. Scien. [3] 9, 421). Properties—Sublimes in yellow needles. M.p. 277°. Very slightly soluble in alcohol and ether, more readily in benzene. Very stable. By treatment with fuming sulphuric acid it is first converted into a monosulphonic acid C,,H,O,-SO,H, and then into a mixture of two disulphonic acids C,,H,O,(SO,H),. By fusion with caustic soda, the monosulphonic acid yields alizarin, the disulphonic acids give isopurpurin and flavopurpurin respectively. DIAZO AND AZO COMPOUNDS By the action of nitrous acid upon the salts of aromatic primary amines and diamines diazo compounds are produced, thus aniline hydrochloride gives diazobenzene chloride C,H,-N:N- Cl, sulphanilic acid gives diazobenzene sulphonic acid Hes ghee benzidine sulphate gives tetrazodiphenyl sulphate ee aoe These reactions take place with extreme readiness, it being only necessary to dissolve or suspend the amine salt or amido- sulphonic or carboxylic acid in water, generally cooled with ice, and add the theoretical quantity of sodium nitrite and hydrochloric acid. The diazo compounds are mostly very unstable bodies, and when dry are explosive. For the preparation of the azo colours they are usually not isolated, but are at once combined with phenols or amines or their sulphonic or carboxylic acids, in alkaline or slightly acid aqueous solution. Thus diazobenzene chloride combines with m-phenylene diamine to form diamidoazobenzene (“ Chrysoidine ”) C,H,:N:N-C,H,(NH,),; diazobenzene sulphonic acid combines with 8-naphthol to form @8-naphtholazobenzenesulphonic acid (“Orange II.”) C,H,(SO,H)-N:N-C,,H,- OH; tetrazodiphenyl sulphate combines with a-naphthylamine sulphonic acid to form “ Congo red.” These bodies are simple oxyazo or amidoazo compounds; in certain cases, however, when the requisite positions are open, more especially with the dioxy-, diamido-, and amidoxy compounds, two diazo residues, similar or dissimilar, can be introduced into the same phenol or amine, producing a disazo compound, thus 2 mols. of diazobenzene chloride will [oe combine with 1 mol. of a-naphthol or with 1 mol. of m-phenylene diamine to form CH, N:N-+C,H(OH)-N:N-CH sorsC HINT CHINE) N:N- CH. Anciier and ‘more important class of disazo colouring matters is obtained by the action of nitrous acid upon certain amidoazo compounds (formed by combining diazo compounds with amines) and combining the diazoazo compound thus produced with another amine or phenol. Thus amidoazonaphthalenedisulphonic acid C,,H,(SO,H), -N:N-+C,,H,- NH,, obtained by com- bining a-diazonaphthalenedisulphonic acid with a-naphthylamine, gives ‘on treatment with nitrous acid the diazoazonaphthalenedisulphonic acid C,,H,(SO,H),-N:N-C,,H,-N:N-OH, ete combines with Q@-naphthol disulphonic acid to form “Naphthol black” C,,H,(SO,H),-N:N-+C,H,-N:N-C,,H,(OH)(SO,H),. The amidoazo compounds employed for the preparation of these disazo colours are themselves colouring matters, but, with the exception of amideazobenzene sulphonic acid, are not used for dyeing. They are usually not isolated, but are converted directly into the disazo compounds in the solution in which they are formed, by further diazotisation and combination with phenols, etc. The following are the most important of the amidoazo compounds employed as intermediate products :— p-Amidoazobenzene O.H;-N:N-C,H,-NH[1:4] i < >—N: Nigeinse Preparation — By slowly running a solution of sodium nitrite (7 pts.) it in water (10 pts.) into a mixture of aniline hydrochloride (26 pts.) dissolved in aniline (50 pts.), agitating and keeping the temperature between 30° and 40°. After the mixture has been kept at 40° for two hours, and has stood for a day at the ordinary temperature, the product is mixed with a slight excess of hydrochloric acid beyond. that required to combine with the aniline, and is diluted with water (250 pts.). The amidoazobenzene hydrochloride which separates as a steel-blue crystalline precipitate is filtered off, washed, and dried. The excess of aniline employed is recovered from the filtrate by making alkaline and distilling with steam (Stidel and Bauer, Ber. 19, 1954). Properties—Orange needles or prisms. M.p. 127°; b.p. above 360°. Nearly insoluble in water, soluble in alcohol, Weak base, its salts, which are sparingly soluble, being decomposed on washing with water. _ Monosulphonie acid C,H,(SO,H) +N: N - C,H,(NH,).—Obtained by sulphonating amido- azobenzene with fuming sulphuric acid at a low temperature, until the product is soluble in alkalies. Small yellowish-white needles, very sparingly soluble in water. Disulphonie acid C,H(SO,H)-N:N - C,H,(NH,)(SO,H).—Obtained by sulphonating amidoazobenzene with fuming sulphuric acid. until the product is easily soluble in water. Steel-blue needles. A mixture of the sodium salts of this and the preceding acid is employed for dyeing under the name of “ Acid yellow.” Amidoazotoluene [2 :1]C,H,(CH,)-N:N - C,H,(CH,)NH,[1 :3 24] Preparation.—By slowly adding a saturated solution of sodium nitrite (1 mol.) to a mixture of o-toluidine (2 mols.) and cone; hydrochloric acid (1 mol.), keeping the temperature at 30° to 40° for several hours. : Properties—Yellow plates or tables. Mp. 100°. Easily soluble in alcohol, nearly insoluble in water. = Sulphome acid, — Obtained by seni amidoazotoluene with fuming sulphuric acid, ——o yt. a. Amidoazoxylene C,H,(CH,),-N : N - C,H,(CH;),NH, Preparation.— By the action of sodium nitrite upon a mixture of m-xylidine and m- xylidine hydrochloride (Nolting and Forel, Ber. 18, 2682). Properties.— Orange-yellow plates. M.p.'78°. Sparingly soluble in cold alcohol, easily in hot. a-Amidoazonaphthalene Preparation.— By mixing equal mols. of a-diazonaphthalene chloride C,,H,- N, - Cl (from a-naphthylamine uence and nitrous acid) and a-naphthylamine i drochiore in cold aqueous solution, then slowly adding sodium carbonate till alkaline. The precipitate is filtered off and crystallised from xylene oo and Church, 4dnn. 129, 108; Friedlander, Ber, 22, 590). Properties.—Brownish-red needles. M.p. 183° corr. . Disulphonie acids C,,H,(SO,H),-N:N-+C,,H,-NH,. Obtained by combining the diazo compounds of the a-naphthylaminedisulphonic acids with a-naphthylamine bydtechionge (Cassella and Co., Eng. Pats. 9214® and 14442), Sulpho--naphthalene-azo-a-naphthylamine 6 CyyHg(SO,H) -N:N-C,H,- NH,[1: 4] Preparation. By combining the diazo compounds of the various sulphonic acids of 8-naphthylamine with a-naphthylamine hydrochloride (Cassella and Co., Joc. cit.). Di-sulpho-benzene-azo-a-naphthylamine [4:2:1]C,H,(SO,H),-N:N- CyH,- NH, [1 : 4] Preparation,—By combining the diazo compound of anilinedisulphonic acid (disulphanilic acid) with a-naphthylamine hydrochloride (Cassella and Co., Eng. Pat. 14442*). Sulpho-y-toluene-azo-a-naphthylamine [4 :2:1] OH,(CH,)(SO,H) -N:N - CH,» NH, [1:4] Preparation.mBy combining the diazo compound of p-toluidine-sulphonic acid with a- naphthylamine. Salicylic-acid-azo-a-naphthylamine [4:3:1]C,H,(OH)(CO,H)-N:N-C,,H,-NH,[1: 4] Preparation.—By combining the diazo compound of amidosalicylic acid with a-naphthy- lamine (Bayer and Co., Ger. Pat. 51504°°; Am. Pat. 438438). _ Properties—Small steel-blue eal Dissolves in alkalies with a yellowish-red eolour. COMPOUNDS OF THE FATTY SERIES Carbonyl Chloride (Phosgene Gas) COC], ic. O=C=Cl, Preparation By leading a mixture of equal volumes of carbonic oxide and chlorine over a condensing surface such as platinised pumice, animal charcoal, etc. (Paterno, Jahresber. 1878, 229). Properties.—Pungent-smelling liquid, gaseous at ordinary temperatures. B.p. 8° corr. ; sp. gr. at 0°=1-392. Very soluble in benzene. Very slowly decomposed by cold water, quickly by hot into carbonic acid and hydrochloric acid. Thiocarbonyl Chloride (Zhiophosgenc) CSCI, 7.6, S=C—Cl, Preparation.—Chlorine is passed into cold carbon disulphide containing a trace of iodine until the liquid has increased in weight by 230// (a2. 5 Cl to CS,). The product CCl, - SCl is purified by distillation with steam and fractionation, and is converted into thiocarbonyl chloride by reduction with stannous chloride or with iron and acetic acid (Klasson, Ber. 20, 2377; Kern and Sandoz, Ger. Pat. 54308). Properties—Reddish liquid of irritant odour. B.p. 74°. On keeping it is slowly con- verted into colourless crystals of the polymeric compound, which melt at 113°. Formaldehyde (Oxymethylene) H,C:0O Preparation. By leading a mixture of methyl alcohol vapour and air in theoretical proportions over heated platinised pumice, charcoal, or coke, contained in a copper tube (Loew, Journ. f. Pr. Chem. 38, 321; Trillat, Ger. Pat. 55176°). Properties.—Pungent-smelling gas. B.p. — 21°. Very soluble in water,in which solvent it is usually collected. On keeping the solution it is slowly polymerised to trioxymethylene O,H,0,, a crystalline solid of m.p. 152°. Valuation—tThe strength of aqueous solutions of formaldehyde can be determined by adding normal ammonia in excess and titrating with sulphuric acid: the quantity of ammonia employed in forming hexamethylenetetramine (CH,),N, gives the percentage of formaldehyde present (Legler, Ber, 16, 1333). Methyl Alcohol (Wood Spirit) OH, - OH Preparation.—From the aqueous portion of the distillate obtained in the destructive distillation of wood, by treatment with lime and rectification. Properties—Colourless alcoholic liquid. B.p. 66°; sp. gr. at 15°=-799. Miscible with water. geet Valuation.—The purity of methyl alcohol, for use in the preparation of dimethylaniline, is of great consequence, especially in regard to freedom from acetone, 957 of it should distil within one degree, and its specific gravity should be correct. It should remain colour- less when mixed with strong caustic soda, and only give a light yellow colour with twice its volume of cone. sulphuric acid. It should not at once decolourise 4 of its volume of a 0-17 solution of potassium permanganate. It should not contain more than 4}, to 17% of acetone, eo | as determined by the following method :—1 to 2 cc. of the methyl alcohol are put into a stoppered flask, and mixed with 20 to 30 ec. of normal caustic potash solution (free from nitrite). 20 to 30 cc. of 4 normal iodine solution are then dropped in, and after shaking for 4 minute the clear solution is acidified with a quantity of dilute hydrochloric acid of sp. gr. 1°025 equal in volume to the caustic potash solution employed. A measured excess of =, normal sodium thiosulphate is then added, and the latter is titrated back with 7 normal iodine solution and starch. From the amount of iodine solution used up the per- centage of acetone is calculated, since 1 mol. of acetone requires 6 atoms of iodine to convert it into iodoform, ie. 1 ec. of ¥ iodine solution is equivalent to "°28 grms. of acetone (Messinger, ber. 21, 3366). Methyl Chloride CH,Cl Preparation —Trimethylamine, obtained from the residues of beetroot molasses by dis- tillation with lime, is heated with hydrochloric acid under pressure (Vincent, Ding. Pol. J. 230, 270; 234, 294; Jauhresber. 1878, 1135). Properties.—Colourless gas of pleasant ethereal smell. Under a pressure of 4 to 5 atmospheres it is liquid at ordinary temperatures. B.p. —21°. Very soluble in alcohol, only slightly in water. Ethyl Bromide C,H,Cl Preparation —Cone. sulphuric acid (2 pts.) is mixed with 96% alcohol (1 pt.), and after standing for some time is diluted with water (4 pt.). Potassium bromide (1 pt.) is then added, and the mixture is slowly heated, finally to 130°. The ethyl bromide, which distils over, is washed with water, and is freed from 7 or 87 of ether, which it contains, by shaking with cone. sulphuric acid in which only the ether dissolves (Ding. Pol. J. 229, 284). Properties,—Colourless ethereal liquid. B.p. 38°; sp. gr. at 15°= 1-476. Succinic Acid CO,H - CH, - CH, - CO,H Preparation—By the dry distillation of amber at 280°; or by the fermentation of a solution of ammonium tartrate at 25° to 30° (Konig, Ber. 15, 172). Properties—Colourless monoclinic prisms. M.p.180°; b.p. 235°. At its boiling point it is converted into the anhydride GH ' a . ’ ’ ‘ i COLOURING MATTERS I. NITRO No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 1 Picric Acid.* Symmetrical trinitro- C,H,N,O, [1] OH Carbazotic Acid. phenol. C,H, { [2] NO, [4] NO, [6] NO, 2 | Victoria Yellow.t Mixture of the C,H,N,O,K [1] OK [1] OK English Yellow. ide! vai age oe [2] CH, and C,H, < [4] CH, . : ium) salts of dinitro- Victoria Orange. o-cresol and dinitro- ( (NO,), 2)2 Saffron Substitute. p-cresol. Aniline Orange. 3 Flavaurin. Ammonium salt of C,H1)N,0,9 [1] ONH, New Vellow.[B.K.]| _ ‘initrophenol-p- cH, J [2] NO, (No longer in com- sulphonic acid. 62) [6 NGS merce. ) [4] SO,NH, 4 | Salicyl Yellow A. | Bromonitrosalicylic C,H, BrNO, CO,H [1] (No longer in com- acid. Cy H,Br( (NO,) OH [2] merce. ) 5 Salicyl Orange (Sodium salt of bromo-| C,;HBrN,O,Na CO,Na [1 (No longer in es dinitrosalicylic acid. E he ie C,HBr(NO,), ONa i merce. ) 6 Zinalin. Probably nitrated CopHygN20, (2) (No longer in com- rosolic acid. merce. ) 7 | Palatine Orange. | Ammonium salt of CyeHaeN;0;, C,H,(NO,). - ONH, [4] (No longer in com- | tetranitro-y-diphenol. , [1] | merce. ) C,H,(NO,), - ONH, [4] 8 | Martius Yellow. | Ammonium, sodium, | Ammonium salt : Free acid : Primrose. Jaune d'or. Manchester Yellow. Naphthol Yellow. or calcium salt of dinitro-a-naphthol. C, pH N30; Sodiwm salt : C,)H,;N,0,Na+ 1s he) Calcium salt : Cop Hy oN 40, 90a C(OH) ss (NO,) ee C(NO,) : ibs * Echurin of the Leeds Manufacturing Co., Brooklyn (Ger. + The colouring shatter known as Victoria Orange consists chiefly of an alkaline salt of dinitro-o-cresol COLOURS. e | Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties, Method of Preparation. | Discovery. Literature. Method of Teplice padent im Action of nitric acid upon IWATA WoOUuLFE. Appearance of dyestuff: light yellow erystals.—In water: spar- phenol or upon phenolsulphonic (from indigo.) ingly soluble in the cold, more easily on boiling. Soluble in alcohol, acids. 1842. LAURENT. benzene, etc. Melts at 122°°5. Tastes bitter.—On boiling with (from phenol.) potassium cyanide: brown solution.—Dyes: wool and silk green- Ann. (1843) 43, 208. ish yellow from an acid bath, 1869. R. Scumirt and L. Guurz. (from phenolsulphonic acids.) Ber. 2, 52. Action of nitric acid upon a 1869. MITTENTZWEY. Appearance of dyestuff : reddish yellow powder.—In water: soluble mixture of the sulph onic acids Wagner’s Jahresber. 15, 593; with orange yellow colour.—On addition of hydrochloric acid : Ber. (1869) 2, 206, 581; (18738) 6, to aqueous solution: white precipitate of dinitrocresol.—On of o- and p-cresol, or upon 974; (1874) 7, 176; (1875) 8, 685; aa : Pree diazotoluene. (1881) 14, 567, 898, 986 ; (1882) 15s addition of caustic soda to aqueous solution: no change of 1858 ; (1884) 17, 370, 608; (1885) colour.—On heating the powder: the potassium salt deflagrates, 8, 252. the ammonium salt burns quietly.—In conc. sulphuric acid: light yellow solution.—Dyes: wool and silk orange. Used for colouring liqueurs, butter, ete. Action of nitric acid upon 1883. LerezicER ANILIN FABRIK | Appearance of dyestuff: yellowish red powder, does not deflagrate mononitrophenol-p-sulphonic BEYER and KEGEL. on heating, but swells up.—In water: easily soluble with a yellow acid. Ger. Pat. 27271 (lapsed). colour.—On addition of hydrochloric acid to aqueous solution: claret red colour, no precipitate.—On addition of caustic soda to aqueous solution: becomes rather darker and smells of ammonia. Zinc dust and caustic soda: on boiling decolourised ; the solu- tion becomes brown on exposure to air.—In conc. sulphuric acid: claret red solution, which becomes colourless on dilution with water.—Dyes: wool and silk yellow. Action of dilute nitric acid 1880. CHEM. FABRIK AUF ACTIEN | Appearance of dyestuff: yellowish white powder, melts on platinum upon monobromosalicylic acid. vormM. HE. SCHERING. foil and burns quietly.—In water: very sparingly soluble ; dis- Ger. Pats. 15117 and 15889 solves in alkalies.—Dyes: wool and silk yellow from an acid bath. (both lapsed). Action of nitric acid upon 1880. CHEM. FABRIK AUF ACTIEN | Appearance of dyestuff: orange yellow powder; smells of bromine ; bromosulphosalicylic acid. vorm. EK. SCHERING. deflagrates on heating.—In water: orange yellow solution ; easily Ger. Pats. 15117 and 15589 soluble in aleohol.—On addition of hydrochloric acid to aqueous (both lapsed). solution: white precipitate of the free acid.—On addition of caustic soda to aqueous solution: colour not altered.—Dyes: wool orange from an acid bath. Action of nitrous acid upon 1870. M. VoGEL. Appearance of dyestuff: orange red powder, insoluble in cold, rosaniline in alcoholic solution. Die Entwicklung der Anilin- sparingly soluble in hot water, easily in alkalies. Was used asa Industrie. 2. Auflage. wood stain. Leipzig 1870, p. 100. Action of nitric acid. upon 1869. ETE CARO. Appearance of dyestuff : brown powder, easily soluble in water.— tetrazodiphenyl (diazotised await and Addition of acids to the aqueous solution: precipitates brown benzidine). sf an flocks which contain the tetranitro-y-diphenol of m.p. 220°.—On G. ScHULTz, heating the powder: does not deflagrate.—Dyes: wool and silk Ann. (1881) 207, 335. orange yellow. Used for paper-staining. Action of nitric acid upon 1864. Marrivs. Appearance of dyestuff: Ammonium and sodium salts, small a-naphthylamine, a-diazonaph- thalene, a-naphthol, or (usual method) upon the (1:2: 4) disulphonic acid of a-naphthol. | Zeits. f. Chem. (1868) 4, SO. DALE, Caro, and MARTIUvs. Eng. Pat. 27855, BALLO. Ber. (1870) 3, 288. DARMSTADTER and WICHELHAUS. Ber. 2, 113; Ann. 152, 299. F. BENDER. Ber. 22, 996 (note). Pat. 2618683 lapsed), is a mixture of picric acid and nitroflavine. (in.p. 86°), whilst in the less soluble Saffron Substitute the dinitro-p-cresol (in.p. 83°°5) predominates. glistening orange yellow plates, calcium salt yellowish red crystals. —In water: soluble with a yellow colour; the ammonium salt is also soluble in alcohol.—Addition of hydrochloric acid to the aqueous solution: precipitates dinitronaphthol of m.p. 138°.— On heating: the sodium salt deflagrates, the ammonium salt burns quietly.—Dyes: wool golden yellow from an acid bath. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 9 Sun Yellow. Sodium salt of C,)H,N,O,Na C,)H,(NO,),ONa a Heliochrysine. tetranitro-a-naphthol. (No longer in com- merce, ) 10 |Naphthol Yellow S. Sodium (or potassium)| C,)H,N,O,SNa, C(ONa) : C(NO,) [ BJ salt of dinitro-a- C,H,(SO,Na) Naphthol Yell naphthol-S-mouo- mie C(NO,) : CH Agi = fe ae sulphonic acid. (NO,) c ellow wv. Citronine A. [Z.] [ONa : NO, : NO, :SO,Na=1:2:4:7] 11 | Brilliant Yellow. Sodium salt of C,)H,N,0,SNa C(OH) See [Sch. ] dinitro-a-naphthol- |: C.H,(SO Nay : r : 3 Naphthol Yellow, “° es C(NO,) : Mp RS. [ By. | [OH : NO, : NO, :SO,Na=1:2: 4; 8] 12 | Gitronine. [B.S.S.]| Mixture of tetranitro- @eHEN:O C,H,(NO C,H,(NO (No longer U oan diphenylamine with are oe NH Oro: OHa (dlisazo-a-naphthol. on oN 3 81 | Orange RR. [/.] Sodium salt of C,H, .N,0,SNa C,H,(CH,),(SO,Na) — N= N — C,H, OHB Orange R. [B.] sulphoxylene-azo-6- naphthol. 82 Luteoline. Sodium saltof | 0, )H,,N,0,9Na [5] SO,Na (No longer in com- sulphoxylene-azo- : [4] CH, merce.) diphenylamine. C,H, [2] CH * The sulphonie acid of metanil yellow comes into commerce as Metanil Yellow 8 [0.]. Metanil Orange I. and II. [/.] are — [ #9 Method of Preparation. Shade and Dyeing Properties. Year of Discoverer. Patents. Behaviour with Reagents. . Diazo pomponnd Faiisnad oaths Discovery. Literature. Method of Employment. p-Sulphanilic |Diphenylamine.| 1876 P. Grizss. O. N. Wirt. | Appearance of dyestuff: orange yellow plates or yellow powder.— acid. Ber. (1879) 12, 262. In water: orange yellow solution; the colour crystallises out : 1877 Z. ROvUSSIN. from the hot aqueous solution on cooling in orange spangles.—On addition of hydrochloric acid to aqueous solution: violet pre- cipitate.—On addition of caustic soda to the aqueous solution : yellow precipitate.—In conc. sulphuric acid: violet solution ; violet: precipitate on dilution with water.— Dyes: wool orange yellow from an acid bath. m-Sulphanilic |Diphenylamine.| 1879 Fr. BAYER & Co. Appearance of dyestuff: brownish yellow powder.—In water: acid. Eng. Pat. 122679, orange yellow solution.—On addition of hydrochloric acid to 1882, Ep. Herp. K. OFHLER. the aqueous solution : magenta red colour, with separation of a Eng. Pat. 4966® (lapsed). precipitate.—On addition of caustic soda to the aqueous solu- tion: no change.—In cone. sulphuric acid: violet solution : magenta red on dilution,—Dyes: wool orange yellow from an acid bath. Sulphonation of Orange IV. Dart & Co: Appearance of dyestuff : orange yellow powder.—In water : yellow Ger. Pat. 210938. solution.—On addition of hydrochloric acid: solution becomes violet red.—Caustic soda: small quantity, no change; excess, violet red colour.—In conc. sulphuric acid: bluish red solution ; magenta red on dilution.—Dyes: wool and silk yellow. o-Toluidine- B-Naphthol. R.. NrerzK1. Appearance of dyestuff: brick-red-powder.—In water: orange monosul phonic Organ. Farbstoffe (1886), 49. . solution.—On addition of hydrochloric acid to aqueous solu- acid: O. MUHLHAUSER. - ~ tion: yellowish brown flocks.—On addition of caustic soda: Ding. Pol. J. 264, 181, 238. solution becomes reddish brown.—In cone. sulphuric acid: ma- J. Soc. Chem, Ind, (1887) 591. genta red solution ; yellowish brown flocks on dilution with water. Dyes: wool orange from an acid bath. p-Toluidine-o- Diphenylamine. 1878 Z. Rovussin: Appearance of dyestuff: orange powder.—In water: yellow solu- sulphonic acid. Eng. Pat. 449178, tion.—On addition of hydrochloric acid to the aqueous solution : steel blue precipitate:—In cone. sulphuric acid: bluish green solution ; steel blue precipitate on dilution with water.—Dyes : wool orange from an acid bath. 2 mols. 1 mol. 1879. L. LiImpPacH. Appearance of dyestuff: dark brown powder. —In water: brown xylidine-sul- a-naphthol. Meister, Lucius, and solution.—On addition of hydrochloric acid to the aqueous phonic acid. BRUNING. solution : violet precipitate—On addition of caustic soda: the aqueous solution becomes orange.—In conc, sulphuric acid : violet solution ; red on dilution with water.—Dyes : wool brownish red from an acid bath. Xylidine-sul- B-Naphthol. L877 Bap. Anin. & SopsA Appearance of dyestuff: bright red powder.—In water: orange phonic acid. FABRIK. solution.—On addition of hydrochloric acid to the aqueous O. MUuLuHauser. , solution: brownish red precipitate. —On addition of caustic Ding. Pol, J. 264, 181, 2388. soda: solution becomes brownish yellow.—In cone. sulphuric J. Soc. Chem. Ind, (1887) 591. acid: cherry red solution; brown precipitate on dilution with water.—Dyes : wool orange from an acid bath. m-Xylidine- Diphenylamine. 1883. O. N. Wirt. Appearance of dyestuff: orange yellow powder.—In water: spar- sulphonic acid. ingly soluble with orange yellow colour.—On addition of hydro- chloric acid to the aqueous solution: violet precipitate. —On addition of caustic soda to the aqueous solution : orange yellow precipitate.—In cone. sulphuric acid; yellowish green solution : violet precipitate on dilution with water.—Dyes.; wool orange from an acid bath. obtained by the action of m-diazobenzene-sulphonic acid upon «- and @-naphthol respectively ; cf. P. Griess, Ber, (1878) 11, 2197. Commercial Name. Scientific Name. Empirical Formula. | Constitutional Formula. 83 Fast Brown N. [B.] | Sodium salt of Cy pH, sN,0,8Na Es i, { [4] 8053 A : | ?- sulphonaphthalene- | C,H, r ‘ St il Katee azo-a-naphthol. \DIN=N-]C 84 Fast Red. Sodium salt of CopH,,N,0,SNa CH. f [4] SO,Na Fast Red A. (Bee eel 106 | [1] N=N -[1] CH, [2] OH Roccelline. [D).H.] ; Rauracienne. Ceracine. Orcelline No. 4. Rubidine. 85 | Azorubine S. [A.] Sodium salt of C,)H,.N,0,8,Na, 4]SO.Na Fast Red 0. [B.] p-sulphonaphthalene- i Cgite { ie N ge N —[2] C, 9H, f (10H nae azo-a-naphthol-p- 10S) | [4 S0n Carmoisine. | By. ] Aine acid, Azorubine A. [C.] | Azo Acid Rubine. [D.] 86 eine 3 BX. Sodium salt of C,)H,.N.0,8,Na, 4|S5O0,Na Croc [Ph 7 p-sulphonaphthalene- 2 z Cy H, { 7 Noe [1] C,,H f [2] OH Yr azo-6-naphthol-mono- Ue? 7} [BBC s sulphonic acid. 87 | Fast Red FE. [B. Sodium salt of Go His N cesses 4] SO,Né [By.] LB) p-sulphonaphthalene- ils Pe PY Cy He ae N oe fikGeee [2] OH g azo-8-naphthol-mono- 10 [6] SO,Na Fast Red. [4.] sulphonic acid. 88 | New Coccine. [A.]| Sodium salt of op Ha Ne Qype nite C,H, { [4] SO,Na [2] OH Brilliant Scarlet. |? *Uphonspihthalenc: | [1]N=N-[1] C,H, 4 [6]SO,Na (! azo-B-naphthol- | 81SO'N Cochi [ - ALR disulphonic acid. ]SO;Na ochinea, e : [B.] 89 | Fast Red D. [£.] Sodium salt of Jopthy oO rptgtas cy. f [4] 80;Na 2] 0H Bordeaux S. [A. | p-sulphonaphthalene- 196 | (1] N=N-[1] C,H, 4 [3] 80,Na azo-B-naphthol- | fe 9 0, °N Patere [M.] disulphonie acid. [6] > Azo Acid Rubine 2B. [D.] Fast Red EB. [B.] 90| Scarlet 6 R. Sodium salt of | C,H, )N,0,,8,Na 4] SO,Na Ponceau 6 B p-sulphonaphthalene- a Cio, { Hi N Bis N-C..H OHB ] aes azo-B-naphthol- "8 1 (SO Nails [AZ] [B.] trisulphonie acid. 91 | Acid Brown R. Sodium salt of C,.H,,N,0,5Na CH [4] SO,Na Al] p-sulphonaphthalene- ry 1o'6 | [1] N=N. [1] NH [ azo-phenylene- C,H a _ azo-phenylene O,H, -N= x 2| [3] NH diamine-azo- benzene. 6 2 ey Ds ee Tee SS ee ee ‘Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties, Diazo Eaigaund Ge Minmicnitk Discovery. Literature. Method of Employment. Naphthionic a-Naphthol. 1878. H. Cano. Appearance of dyestuff: brown powder. —In water: yellowish acid. Bap. Antn. & SopA brown solution.—On addition of hydrochloric acid : the aqueous FABRIK. solution becomes magenta red. —On addition of caustic soda: Eng. Pat. 78678 (expired). the solution becomes reddish brown.—In cone. sulphuric acid : Am. Pat. 204799 (expired). violet solution ; magenta red on dilution with water.—Dyes : wool Ger. Pat. 541178, brown from an acid bath, Naphthionic B-Naphthol. 1877 H. Cano. Z. Rousstn, | Appearance of dyestuff: brownish red powder.—In water: spar- acid. Bap. ANIL. & Sopa ingly soluble cold, more easily hot, with a red colour.—On addi- FABRIK. tion of hydrochloric acid to the aqueous solution: yellowish Eng. Pat. 78678 (expired). brown precipitate.—On addition of caustic soda to the aqueous Am. Pat. 204799 (expired). solution : the colour becomes rather duller and darker.- In conc, Ger. Pat. 541178. sulphuric acid: violet solution; yellowish brown precipitate on Fr. Pat. 12314878, dilution with water —Dyes : wool red from an acid bath. P. Gress. Ber. 11, 2199; 12, 1364. K. RovusSsEL. Monit. de la teinture (1883), 271. Naphthionic a-Naphthol- 1883. O. N. Wirt: Appearance of dyestuff: brown powder.—In water: magenta red acid. monosulphonic VEREIN. CHEM. FABRIKEN solution.—On addition of hydrochloric acid to the aqueous acid NW. MANNHEIM. solution : brown gelatinous precipitate.—On addition of caustic Eng. Pats. 22378? and 423783, soda: the solution becomes rather yellower.—In conc. sulphuric Ger. Pat. 2601283, acid: violet solution; magenta red on dilution with water.— ; ‘ Dyes ; wool red from an acid bath. Naphthionic B-Naphthol- 1882. EuGcEen FRANK. Appearance of dyestuff : scarlet red powder.—In water : yellowish acid, sulphonic acid Fr. Bayer & Co. red solution.—On addition of hydrochloric acid to the aqueous aor B. Eng. Pat. 20308, solution : no change.—On addition of caustic soda: the aqueous Am. Pat. 256376. solution becomes yellowish brown.—In conc. sulphuric acid: Ger. Pat. 2040282. reddish violet solution ; yellowish red on dilution with water.— Dyes : wool red from an acid bath. Naphthionic B-Naphthol- 1878 Bap. ANIL. & Sopa Appearance of dyestuff: reddish brown powder.—In water: bor- acid. monosul phonic FABRIK. deaux red solution.—On addition of hydrochloric acid to the acid S. Eng. Pat. 78678 (expired), aqueous solution: no change.—On addition of caustic soda: Ger. Pat. 541173, solution becomes brown.—In conc. sulphuric acid : violet solu- tion ; red on dilution.—Dyes : wool red from an acid bath. Naphthionic B-Naphthol-di- 1878 ACTIENGES. F. ANILIN- Appearance of dyestuff ; ‘scarlet red powder. — In water: easily acid. sulphonic acid FABRIKN. soluble.—On addition of hydrochloric acid to the aqueous solu- Meisrer, Luctus, & tion : nochange.—On addition of caustic soda : solution becomes Brunina. brown.—In cone. sulphuric acid : magenta red solution ; yellow- En g. Pat. 81684, ish red on dilution.—Dyes : wool red from an acid bath. Am, Pat. 314938. Ger. Pat. 364918. ioni 2-Napl -di- ee Meisrer, Lucius, & Appearance of dyestuff: reddish brown powder.--In water: ma- a aa ee a Brixinc. | genta red solution.—On addition of hydrochloric acid to the Ger. Pat. 322978 aqueous solution : no change.—On addition of caustic soda to the aqueous solution: colour becomes darker.—In cone. sul- phuric acid: violet; magenta red on dilution with water.—Dyes : wool red from an acid bath. ionic S 4 - 1H. Appearance of dyestuff: brown powder.—In water: magenta red Bepethionie Eh ala ‘ peet. eg es & solution.—On addition of hydrochloric acid to the aqueous acid. EP fs 2 z BRGNiG we solution: no change.—On addition of caustic soda: solution pe Env. Pat. 254482 (lapsed). becomes reddish brown.—In conc. sulphuric acid : violet solu- Ber Pat. 268506. tion ; magenta red on dilution.—Dyes : wool red from an acid bath. Ger. Pat. 220388. me ie ass ys } . Appearance of dyestuff: brown powder.—In water: brown solu- Beer cuionic oo ae AcT Cae a he ILIN- ee ae addition of hydrochloric acid to the aqueous solution : FABRIKN. Ger. Pat. 22714 (lapsed). Chem, Ind. (1883) 6, 207. M brown precipitate.—On addition of caustic soda: no change.— In conc. sulphuric acid: dull olive green solution ; brown pre- cipitate on dilution.—Dyes : wool brown from an acid bath. Scientific Name. Empirical Formula. Constitutional Formula. No.} Commercial Name. 92) Acid Ponceau. ee Cy9H,,N,0,SNa C,H, tn Na su onaphtnaiene- 10 bored Se oe SHAWL =N— [1] Cob eeeee 93 | Fast Brown 3 B. ig arena Coots Nea. | C,H f [6] SO. oe [4.] eka *\ [2] N=N—[4] C,,H, [1] OH 94 | Double Brilliant Seta CypHy3N,0,5Na CH ee SO,Na Scarlet @. [4°] | ovanaphihel we BN =N [1] CoH [2] OH 95 | Double Scarlet Sodium salt of Coots No Oven ide an Extra 8. [41] sulphonaphthalene- eC a a C,H, ve S08 a [2] C,H, [1] OH Double Brill azo-a-naphthol- Jy s SO,Na g ae A etry eae monosulphonic acid. carle . [By. Brilliant Ponceau 4 R. [By.] 96 | Pyrotine RRO. Sodium salt of OG; H.eN.O;S,Nas 5]SO,Ne aa [D.] sulphonaphthalene- 20a 2h 728g C,H, { ee hee pers [2] C,.H,. [1] OH ; azo-a-naphthol- 10 a SO,Na monosulphonie acid. 97 | Milling Yellow. Sodium salt of C,/H,,N,O.SNa. : DI sulphonaphthalene- ie a eae CioH eee Be 4] C,H, [108 : azo-salicylic acid. [ ] [2] CO,Na 98 | Yellow fast-to- eure salt of Cig, NeOeNe CH oe CO,Na m-carboxybenzene-azo- ; BE Saami ce ont sede bae WN au-savon. [P.] 99 | Clayton Yellow. sae salt ue Cog oN Ss 0,Na, [4] CH [Cl. Co.] BEES ETD teat ee C,H, 3 [1] Nae SO.Na : peice compound of C [4] C,H, 2 Turmerine. [B.S.S.] dehydrothiotoluidine- [2] a= U4] [1]N ee Yellow. sulphonic acid. By.) [2] Ss NH-N Reel nC [4] CoH | So,Na [4] CH, 100 Mimosa. [(@. | Shade and Dyeing Properties. Method of Preparation. : : ; F Year of Discoverer. Patents. 3ehaviour with Reagents. em poand Suinhined with Discovery. | Literature, : Method of Employment. 6-Naphthyl- B-Naphthol. L. Du RAND, HUGUENIN Appearance of dyestuff: scarlet red powder.—In water: soluble famine sulphonic Seco: in hot water, sparingly in cold.—On addition of hydrochloric 4 acid (chiefly acid to the aqueous solution : brown precipitate.—On addition a and y). of caustic soda: the solution becomes browner.—In conc. sul- phuric acid : magenta red solution; brown precipitate on dilution with water.—Dyes: wool red from an acid bath. sts B-Naphthyl- a-Naphthol. 1882, H. Prinz. Appearance of dyestuff : brown.—In water : brownish red solution. amine mono- FARBFABRIK VORM. On addition of hydrochloric acid to the aqueous solution: red- sulphonic acid BrRONNER. dish violet.—On addition of caustic soda to the aqueous solu- Br. Eng. Pat. 3727 82. tion: magenta red.—In conc. sulphuric acid: blue; reddish Ger. Pat. 22547°. violet precipitate on dilution.—Dyes: wool brown from an acid bath. B-Naphthyl- B-Naphthol. 1882. H. Prrvz. Appearance of dyestuff: reddish brown powder.—In water : scarlet _ | amine mono- FARBFABRIK VORM. solution. —On addition of hydrochloric acid to the aqueous sulphonic acid BRONNER. solution: brown precipitate. —On addition of caustic soda to : Br, Eng. Pat. 872482, the aqueous solution: reddish brown precipitate, soluble in Ger, Pat. 225478, much water.—In conc. sulphuric acid: magenta red solution ; brownish red precipitate on dilution with water.—Dyes: wool a yellow scarlet from an acid bath. | B-Naphthyl- a-Naphthol- 1882. HH. PRinz, Appearance of dyestuff: brownish red powder.—In water : yellow- amine mono- | monosulphonic FARBFABRIK VORM. ish red solution. —On addition of hydrochloric acid to the . sulphonic acid acid NW. BRONNER. aqueous solution: yellowish brown precipitate. —On addition 3 Br, Eng. Pat. 372482. of caustic soda: no change.—In conc. sulphuric acid: magenta . Ger, Pat. 225478, red solution; scarlet on dilution.—Dyes: wool scarlet from an acid bath, : B-Naphthyl- a-Naphthol- 1884, Daunt & Co. Appearance of dyestuff : brownish red powder.—In water : yellow- | amine mono- monosulphonic Eng. Pats. 7712, 7713°', ish red solution.—On addition of hydrochloric acid: solution . sulphonic acid acid NW. 11002%4, becomes bluer.—On addition of caustic soda: solution becomes | D (chiefly +). Ger. Pats. 290848, 322715, yellower.—In conc. sulphuric acid: magenta red solution; on : 3227684, dilution with water, red.—Dyes : wool red from an acid bath. : B-Naphthyl- | Salicylic acid. Appearance of dyestuff: yellow powder.—In water: yellow solu- | amine mono- tion.—Addition of hydrochloric acid: solution brown, deposit- sulphonic acid, ing after some time a brown precipitate.—On addition of caustic ¢ soda: the solution becomes deep orange red.—In conc. sulphuric acid: yellowish red solution.—Dyes: wool yellow from an acid =. bath ; chromed wool yellow, fast to milling and light. 4 | m-Amido- Dipheny]l- 1884. ROSENSTIEHL. Appearance of dyestuff: brown paste.—In water: slightly soluble. benzoic acid. amine, Soc. ANON. DES Mat. Conor. On addition of hydrochloric acid to the aqueous solution : red- ET DES PRODUITS CHIM. dish violet colour.—On addition of caustic soda to the aqueous DE St. Denis. solution : scarcely any change.—In cone. sulphuric acid : violet Eng. Pat. 462188, solution; magenta red on dilution.—Dyes: wool orange from a Am. Pat. 157755. Soap bath, Ger. Pat. 29991°. Dehydro- Dehydro- 1887. A. G. GREEN and Appearance of dyestuff: yellow powder.—In water : yellow solu- | thiotoluidine | thiotoluidine F. EVERSHED. tion.—In alcohol: yellow solution.—On addition of hydro- | sulphonic acid. | sulphonic acid. 1888. W. PFITzINGcER. chloric acid to aqueous solution: reddish yellow precipitate.— 1889. Pu. BRUNNER and J. HALL. On addition of caustic soda: orange yellow coloration and Tur CLAYTON ANILINE Co. precipitate.—In conc. sulphuric acid : brownish yellow solution ; Eng. Pat. 1420789 on dilution the colour becomes paler, but does not precipitate.— ¥. Bayer & Co. Dyes: unmordanted cotton bright yellow from an alkaline bath. Eng. Pat. 18354. Am. Pat. 428629. Ger. Pat. 5393559, y Boiling the diazo-compound of 1890. Cy. Ris. Appearance of dyestuff: yellowish brown powder.—In water: primuline with aqueous ammonia. J. R. Guicy & Co. Eng. Pat. 1771%. Am. Pat. 440281%. Ger. Pats. 53666” and 56593”, yellow solution. —On addition of hydrochloric acid to the aqueous solution: orange yellow precipitate.—On the addition of caustic soda to the aqueous solution : orange red precipitate. In conc, sulphuric acid : yellow solution ; on dilution with water, brownish precipitate and evolution of nitrogen.—Dyes : unmor- danted cotton yellow from a neutral or alkaline bath. [ 84 ] No.| Commercial Name. Scientific Name. Kympirical Formula. Constitutional Formula. 101 Oriol Yellow. Sodium salt of | 1] 0H [G.] primuline-azo-salicylic P—-N=N-[4]C,H, i CO,Na oh acid. (P =the radicle of Primuline.) 102 A i salt of Co PLN | Olas Sere ean tet euphencinesy anion a geal ee ee [Cl. Co.] I J H,4[2]S & [4] N= Nee [1] C,H. [210 ia thiocresol-azo-B- 3 10°"6 naphthol. [4]CH, 103| Alkali Brown. Sodium salt of P—-N=N-C,H,(NH,), [1: 2 : 4] LD.] primuline-azo- = : phenylene diamine. 104| Atlas Red. [B.S.5.] < Sodium salt of P—-N=N-C,H,(CH,)(NH,).[1:3: 4:6] primuline-azo-tolylene diamine. 105} Clayton Cotton Sodium salt C.,H»,N,O,S.aNa, CH, Brown. [C1. Co.] of sulphobenzenyl- pig BEES ES an (3) Se SO,Na "ho" "=| amido-thiocresol-azo- Na = O[1]C,H { 4 os phenylene-diamine- [1] [4] Noo H,(NH,) azo-naphthalene- CH [1]JN=N aaa a sulphonic acid, 106 \[4]SO,Na 106; Terra Cotta F. Sodium salt P- i N Y of primuline-azo- { : >C, HNH,), a phenylene-diamine- Cio (80, Na azo-naphthalene- sulphonic acid. 107 | Curcumeine.* [. A.| Mixture of nitrated New Yellow diphenylamine yellow T. M. : with nitro- on : .] diphenylamine. 1tronine. 108} Azo Acid Yellow. | Mixture of nitrated [ A] diphenylamine yellow with nitro- oe i diphenylamine. Indian Yellow. [By.] 109 Terra Cotta R. Nitro-oxy-azo- C,,H,N,O;Na OH [G.] benzene-carboxylic . C,H, -N=N-O,H,4 CO,H 7 ) J a acid. lwo (2) 2 110| Persian Yellow. | Nitro compound of C,,H,)N,0,Na OH G zen | HCH) N= — OH} CO,H alicylie acid. f y NO, (?) * By the action of nitrie acid upon diphenylamine-yellow, Curcumeine Eee | Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. |p; Discovery. Literature. Method of Employment. pine Barend Combined with y : ee a Primuline or | Salicylic acid. 1888, J. R. Garey & Co. Appearance of dyestuff: red powder.—In water: orange yellow dehydrothio- Am. Pat. 39899088, solution.—On addition of hydrochloric acid to the aqueous toluidine- DaHL & Co. solution: yellow precipitate.—On addition of caustic soda: the sulphonic acid. . Ger. Pat. 4846588, solution becomes rather redder.—In cone. sulphuric acid: scarlet red solution; on dilution brownish yellow precipitate.—Dyes : unmordanted cotton yellow from a boiling alkaline bath. Dehydrothio- B-Naphthol. 1889. Cu. DREYFUS. Appearance of dyestuff: dark red powder.—In water: reddish brown toluidine- Tur CLAYTON ANILINE Co. solution.—On addition of hydrochloric acid to aqueous solu- sulphonic acid. Eng. Pat. 189018. tion: red precipitate. —Dyes: wool and silk red from an acid J. Soc. Dyers and Colorists bath. (1890), 32. Primuline. m-Phenylene 1887, A. G. GREEN. Appearance of dyestuff: dark brown powder.—In water : brownish diamine, Dann & Co. red solution.—In alcohol: brown solution. —On addition of hydrochloric acid to the aqueous solution: dark brown pre- cipitate. —On addition of caustic soda to the aqueous solu- tion: red precipitate.—In conc. sulphuric acid: bluish violet solution; dark brown precipitate on dilution—Dyes: unmor- danted cotton a reddish brown from an alkaline bath. Primuline. m-Tolylene 1889. A. G. GREEN. Appearance of dyestuff: dark red powder.—In water: brownish diamine, Brooker, Srmpson, & red solution.—On addition of hydrochloric acid: dark precipi- SPILLER. tate.—Dyes : unmordanted cotton terra-cotta red from an alkaline Eng. Pat. 10448”, bath. Gives deep ingrain brown shades by diazotisation and development on the fibre. Dehydrothio- p-Sulpho- 1890. Je HATIC Appearance of dyestuff: brown powder.—In water: brown solu- toluidine- naphthalene- CLAYTON ANILINE Co. tion.—On addition of hydrochloric acid to the aqueous solu- sulphonic acid. az0-m-pheny- Hng. Pat. 821 590, tion: brown precipitate.—On addition of caustic soda to the lene diamine. J. Soc. Dyers and Colorists aqueous solution : no change.—In conc. sulphuric acid: violet (1892), 8, 178. solution ; chocolate brown precipitate on dilution with water.— Dyes: unmordanted cotton brown from a salt bath. Primuline. p-Sulpho- 1890. Jon. WALTER. Appearance of dyestuff: dark brown powder.—In water: brown naphthalene- J. R. Griey & Co. solution.—On addition of hydrochloric acid to the aqueous azo-m-pheny- Eng. Pat. 1688. solution : brown precipitate.—On addition of caustic soda: no lene diamine. Am. Pat. 440288%, change.—In conc. sulphuric acid : reddish violet solution ; brown Fr. Pat. 203439%, precipitate on dilution with water.—Dyes: unmordanted cotton brown from a neutral or alkaline bath. Action of nitric acid upon 1880. EK. KNECHT. Appearance of dyestuff: ochre yellow powder.—In water: spar- diphenylamine yellow ingly soluble in cold, more readily in hot.—On addition of hydro- (No 75) chloric acid to the aqueous solution: magenta red colour.— On addition of caustic soda: yellowish brown colour.—In conc. sulphuric acid : reddish violet solution ; olive brown on dilution. —Dyes: wool yellow from an acid bath. Action of nitric acid upon 1880. E. Knecur. Appearance of dyestuff: ochre yellow powder.—In hot water: diphenylamine yellow lemon yellow solution.—On addition of hydrochloric acid: the (No. 75). colour of the solution becomes browner and deeper.—On addition of caustic soda: solution becomes yellowish brown.—In cone. sulphuric acid: magenta red solution; on dilution with water, yellowish brown precipitate.—Dyes: wool yellow from an acid bath. Nitration of benzene-azo- 1888. JoH. WALTER. Appearance of dyestuff: yellowish brown paste or dark brown salicylic acid. J. R. Grriay & Co. powder.—In water: yellowish brown solution (powder),—On Eng. Pat. 13920%. addition of hydrochloric acid to the aqueous solution: light Am. Pat. 431297%. brown precipitate.—On addition of caustic soda: solution be- Fr. Pat. 19319088, comes cherry red.—In conc. sulphuric acid: yellow solution ; light brown precipitate on dilution.— Employment: in calico printing for the production of browns upon a chromium mordant. Nitration of p-toluene-azo- 1888. Jou. WALTER. Appearance of dyestuff: yellow paste or brownish yellow powder. salicylic acid. J. RaGeey &1Cons —In water : yellow solution.—On addition of hydrochloric acid : Eng. Pat. 1392088, light brown precipitate—On addition of caustic soda: the solu- Am. Pat. 431297. tion becomes orange.—In cone. sulphuric acid : orange solution ; Fr. Pat. 19319088. light brown precipitate on dilution.—Employment: in calico f printing for the production of yellow with a chromium mordant. is first formed ; then by further action, Azo Acid Yellow. No. | Commercial Name. 111| Narceine. [D. H.| 112} Azarine S. [J] 113} Sudan III. [A.] 114} Azococcine 7 B. [4.] Cloth Red G. [By.] 115} Croceine B. [Sch.] 116) Ponceau RR. Pee aay (No longer in com- merce. ) 117 | Brilliant Croceine. 118 [C.] Cotton Scarlet. [2] Ponceau SS extra. [4.] Scientific Name. Sodium bisulphite compound of p-sulphobenzene- azo-B-naphthol. Ammonium bisulphite compound of dichloro-phenol-azo- B-naphthol, Benzene-azo-benzene- azo-8-naphthol. Sodium salt of benzene-azo-benzene- azo-a-naphthol-p- sulphonic acid. Sodium salt of benzene-azo-benzene- azo-a-naphthol- disulphonic acid. Sodium salt of benzene-azo-benzene- azo-8-naphthol- monosulphonie acid. Empirical Formula. C,sH,,N,0,S,Na, C, ,H,,C1,N,0,8 Constitutional Formula. [4]SO,Na CH, oe oe N(SO,Na) — [1] C,H, [2] OH C,H, Cl,(OH) — NH — N(SO,NH,) - [1] C,,H, [2]0H Co9H,,N,O Cy H,,N,0,SNa Cy,H,,N,O-S,Na, Sodium salt of benzene-azo-benzene- azo-B-naphthol- disulphonic acid. Sodium salt of benzene-azo-benzene- azo-B-naphthol- disulphonie acid. 119 Ponceau 5 R. [M. | Erythrine X. [D.] Sodium salt of benzene-azo-benzene- azo-B-naphthol- trisulphonic acid. C,H, -N=N-0,H, -N=N-C,,H,- OH - [1]0H (,H,-N=N-¢,8,- Sees CyoHlsff 4180,Na [1] OH C,H, - N=N —C,H, -N=N —[2]C,,H,4[4]5O,Na 8]SO,Na Cy9H,,N,0,SNa 2)0H 164 - 0,H, — N=N+ C,H, == eee Rae CoH, ,N,0,8,Na, [2]0H | C,H, -N=N- 0,H, -N=N-[1]C,,H,4[6]80,Na| O,Na CoH, 4N,0,S,Na, get | [2]0H |) : O,H; -N=N-0,H,-N=N-[1] Colt SO,Nal | [6] SO,Na) F CinH NO poe Nae C,H, -N=N-C,H,-N=N-O oH; ese Na), ; : oe Method of Preparation. : F : Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Diazo Compound | ay np ,,, | Discovery. Literature. Method of Employment. Perth ombined with Sulphanilic B-Naphthol. 1879, PRruD’ HOMME. Appearance of dyestuff: orange yellow powder.—In water : yellow acid, EB. NOTING. solution. —On addition of hydrochloric acid to the aqueous And treatment with sodium Mon. Scien. (1886) 319. solution: no change.—On addition of caustic soda: solution bisulphite, becomes brownish red.—In cone. sulphuric acid: yellowish brown solution ; evolves sulphurous acid on dilution and warming. —Employment: for calico printing. Amidodichloro-| $8-Naphthol. 1883. A. SPIEGEL. Appearance of dyestuff: yellow paste, smelling of sulphurous acid. phenol. Mristsr, Lucius, & —In water : sparingly soluble with a yellow colour.—On addition And treatment with ammonium BRUNING. of hydrochloric acid to the aqueous solution: orange yellow bisulphite. Eng. Pat. 5767%. precipitate.—On addition of caustic soda to the aqueous solu- Am. Pats. 302790 and tion : violet precipitate ; on boiling a red solution.—In cone, sul- 306546. phuric acid : magenta red solution ; reddish brown precipitate on Ger. Pat. 29067®, dilution with water.—Employment : for calico printing. Ber. (1885) 18, 1479. Amido-azo- B-Naphthol. 1879 Fr. GRAESSLER. Appearance of dyestuff: brown powder.—In water: insoluble.— benzene. Ger. Pat. 1648379, In cone. sulphuric acid : bluish green solution; on dilution with R. Nrerzxi. water blue solution and then a red precipitate.—In alcohol: red Ber. (1880) 13, 1838. solution.—Employment ; for colouring oils, varnishes, etc. Amido-azo- a-Naphthol- 1883. OPN, Wirr. Appearance of dyestuff: brown powder.—In water: sparingly benzene. monosulphonic VEREIN CHEM. FABRIKEN. soluble with magenta red colour.—On addition of hydrochloric acid NW. Eng. Pat. 223783, acid to the aqueous solution: brownish red precipitate. —On Ger. Pat. 260128. addition of caustic soda to the aqueous solution: reddish violet precipitate soluble in water.—In conc. sulphuric acid: bluish violet solution ; brownish red precipitate on dilution with water.—Dyes: wool red from an acid bath. Amido-azo- a-Naphthol- 1884, MENSCHING. Appearance of dyestuff: brownish red fpowder.—In water: spar- benzene. disulphon ic THE ScHOLLKOPF ANIL, & ingly soluble with magenta red colour.—On addition of hydro- acid Sch. CHEM. Co. chloric acid to aqueous solution : violet precipitate.—On addi- Eng. Pats. 157758 and tion of caustic soda: solution violet.—In cone. sulphuric acid: 15781®. violet solution; reddish violet precipitate on dilution.— Dyes: Am, Pat. 333037. wool red from an acid bath. Ger. Pat, 40571. Amido-azo- B-Naphthol- 1879. Fr. Baver & Co. Appearance of dyestuff: brown powder.—In water: cherry red benzene. monosulphonic Eng. Pat. 50037. solution. —On addition of hydrochloric acid to the aqueous acid B. and S. Ger. Pat. 1648279, solution : brown flocks soluble in water.—On addition of caustic L. Vienon & J. B. Boasson. soda to the aqueous solution: violet precipitate, soluble in Ber. (1880) 13, 1060. water.—In cone. sulphuric acid : blue solution ; brown flocks on dilution with water.—Dyes: wool red from an acid bath. £ Amido-azo- B-Naphthol- 1882. L. Limpacu. Appearance of dyestuff: light brown powder.—In water: cherry benzene. disulph onic 1883. MEINHARD HOFFMAN. red solution. —On addition of hydrochloric acid to the aqueous acid G (y). Mutstrr, Lucius, and solution: brown precipitate. —On addition of caustic soda: BRUNING. brown solution.—In conc. sulphuric acid: reddish violet solu- Ger. Pat. 36491. tion; on dilution with water, blue and then a brown precipitate. L. CasseLLta & Co. —Dyes: wool red from an acid bath. Eng. Pat. 816°4. 4 Am. Pat. 314939%, e Amido-azo- B-Naphthol- 1879 Fr. BAver & Co. Appearance of dyestuff: brown powder.—In water : magenta red benzene. disulphonic Eng. Pats. 500379 & 536%. solution.—On addition of hydrochloric acid to the aqueous a acid R. Am. Pat. 233465. solution: violet precipitate.—On addition of caustic soda: Ger. Pat. 1648279, solution becomes reddish violet.—In conc. sulphuric acid : violet solution ; violet precipitate on dilution with water.—Dyes: wool red from an acid bath. ‘ | Amido-azo- B-Naphthol- 1881. L. LimpacuH. Appearance of dyestuff: brown powder, — In water : cherry red be benzene. trisulphonic Meister, Lucius, and solution.—On addition of hydrochloric acid to the aqueous a acid. Bruninc. ‘ solution: brown flocculent precipitate.—On addition of caustic Tae £, as — we Eng. Pat. 25448? (lapsed). Am. Pat. 268507. Ger. Pat. 22038. soda: solution becomes brown.—In conc. sulphuric acid : reddish violet solution, becoming first blue and then red on dilution with water.—Dyes: wool bluish red from an acid bath. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 120} Croceine 3 B. Sodium salt of Os,H,.N,0,5,Naz; [Sch. ] toluene-azo-toluene- eee a oae C, .H ave oe C,H (CH, OHa azo-a-naphthol- 3\N=N-O GH, disulphonie acid. \ 104 \(SO,Na), 121} Cloth Red G. [0.] orgs salt of C,H, 9N,0,5Na CH (CH, CH, Cloth Red G extra. toluene-azo-toluene- 6 4\N= N-C 7H, [2] OH Dh azo-8-naphthol- 6“38\N=N-— [1] C,H, {fa [By] monosulphonie acid. [6]SO,Na 122 Cloth Red B. Sodium salt of C,,H,.N,0,S,Na, CH, [0.] toluene-azo-toluene- oe * CH, fe SNe { CH, 2]0H azo-B-naphthol- 3\N =N -[1]C,,H,4[3]SO,Na disulphoniec acid. [6] SO, Na 123} Cloth Red B.* ; oe an of C,,H,5N,0,SNa C,H f CH, D, oluene-azo-toluene- 4 [By.] azo-a-naphthol- ES = eo nee —[2] C,H, ia ye t monosulphonie acid. [4]SO,Na | 124} Cloth Red 3G , sp an of C,,H,,N,0,8Na OH extra. | By. | ole ie de pho fot N—-—C,H, [2] NH azo-B-naphthylamine- ce a 1).C. s{ 2 monosulphonic acid, [1] Cio [6] SO,Na 125| Bordeaux BX. Sodium salt of C,,H.3N,0,SNa CH), [By.] xylene-azo-xylene- ae C,H A BSS. {CBs [2] 0H azo-B-naphthol-f- ay {ij Cy ee te SO, monosulphonie acid. [6] Na 126| Orchil Red A. Sodium salt of C,,H,.N,0-S,Na, CH,), [B ] xylene-azo-xylene- a eae OsHs{ Hee (63; (CH), [2] OH : azo-B-naphthol- 5~?2\N=N [1] C,)H,5 [3] SO,Na disulphonic acid. 6]SO,Na 127 Fast Scarlet. Sodium salt of OC, UaeN OTs Nai. 4]SO.Na { 1 sulphobenzene-azo- gi ee C,H : Double Scarlet. + ee pe B. 4|[1]N=N-O,H, -N=N-[1]C,,8,[2)/0n [K.] naphthol. 128] Croceine Scarlet Sodium salt of C..H,,N,0,S,Na, 4]S80,Ne 3 B. [By] sul phobenzene-azo- sea tate Soils 2H eae Vee ok O,H,-N=N-[1]C,)H, [2]0OH | P ; 4 BB benzene-azo-f- 105 | [8]SO,Na} onceat : naphthol-mono- | [A.] sulphonic acid. * Cloth Red 3 B extra is obtained by combination of diazotise d + Mixed with the sodium salt of the disulphonic eos] Method of Preparation. Year of Discoverer. Patents. piano epeenund Combined with Peay ery, Literature. Amido-azo- a-Naphthol- 1884, MENSCHING. toluene. disulphonic THE ScHéLLKorr ANIL. & acid Sch. Curem. Co. Eng. Pats. 15775 & 15781, Am. Pat. 333087. Ger. Pat. 40571®. Amido-azo- B-Naphthol- 1879. K. OEHLER. toluene. monosulphonic Ger. Pat. 1648279, acid S. Fr. BAYER & Co. Eng. Pat. 5003”. Amido-azo- B-Naphthol- 1879. K. OBHLER. — toluene. disulphonie Ger. Pat. 164827, acid R. Fr. Bayer & Co. Eng. Pats. 5003” and 536%, Amido-azo- a-Naphthol- 1879, K. OEHLER. toluene. monosulphonic Fr. BAYER & Co. acid NW. Ger. Pat. 1648279, Eng. Pat. 5003”. Amido-azo- B-Naphthyl- 1879. C. DuIsBERG. toluene. amine- sulphonic acid Br. Amido-azo- B-Naphthol- 1879. RUBEL. xylene. monosulphonic Fr. BAYER & Co. > acid S. Eng. Pat. 50037. *. R. KrvuGENeER. Ger. Pat. 164827, Amido-azo- B-Naphthol- 1880. SCHUNCKE. xylene. disulphonic Am. Pat, 246221. acid R. BADISOHE ANIL. & SoDA FABRIK. 1879. L. Limpacu, Meister, Lucius, & BRUNING, Eng. Pats. 50037 ; 50217; 536%, Ger. Pat. 220108 ; add. to ' 1648279, | arta H,, 80, {Na : toluene-az0-B- 6 N=N-C,H, CH, [2] 0H eS 6 Ns che [1] C8, 1s 50,Na M4 135| Bordeaux BX. Sodium salt of Cy,Ho2N,0,S.Na, (CH,), [By.] i ey C,H, S0,Na (CH, seieeert w2n-cH,{CO% yg (2108 | 1 Saal S §0,Na | 136| Fast Violet R. Sodium salt of CygH,,N,0,5,Na, [4]SO,Na sulphobenzene-azo-a- eta 4 10 Ek A : [2]0H 4 [By] ihehthalenerarsik Baek N[AIC gH LLIN: N[1]CioH at SO, Na} naphthol-6-sulphonic acid. eek Diazo Compound from Amidoazo- benzene-di- sulphonic acid. Amidoazo- benzene-di- sulphonic acid. Amidoazo- benzene-di- sulphonic acid. Amidoazo- toluene-mono- sulphonic acid. Amidoazo- toluene-mono- sulphonic acid. Amidoazo- toluene-mono- sulphonic acid. Amidoazo- xylene-mono- sulphonic acid. ct ek Dd A es on ae p-Sulpho- benzene-azo- a-naphthyl- amine. Method of Preparation. Combined with B-Naphthol. B-Naphthol- disulphonic acid R. p-Tolyl-B- naphthylamine. a-Naphthol- monosulphonic acid NW. B-Naphthol- monosul phonic acid B, B-Naphthol- monosulphonic acid S. B-Naphthol- monosulphonic acid S. B-Naphthol- sulphonic acid S, Discoverer. Patents. Literature. R. NIerzxk1. Ber. (1880) 13, 800, 1838. R. KRvUGENER. Eng. Pats. 500379 and 529°, Ger. Pat. 1648279. W. v. MILLER. Ber. (1880) 13, 542, 803, 980. KOHLER. Bap, Anin. & Sopa FABRIK. Am. Pats. 2249278 and 22492889, S. PrAarr. W. v. MILLER. Ber. (1880) 13, 542, 803. Chem. Ind. (1880) 3, 173, 203. R. NIEerzki. Ber. (1880) 13, 980, 1838. Chem. Ind. (1880) 3, 203, 388. L. ScHap. ACTIENGESELLSCH. F. ANIL. FABRIKEN. Eng. Pat. 9754°°. Am, Pat. 354746. Ger, Pat. 38425%, VEREIN CuEM, FABRIKEN. Eng. Pats. 223753 and 42378, Ger. Pat. 26012. E. FRANK. Fr. Bayer & Co. Eng. Pats. 12258!, 20308, 241183, Am. Pat. 25638. Ger. Pat. 180278. E. FRANK. Fr. BAYER & Co. Eng. Pat. 5003”. E. FRANK. Fr. BAvEeR & Co. Eng. Pat. 5003”, Fr. BAYER & Co. L. CAssELLA & Co. Ger. Pat. 40977%. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: reddish brown powder.—In water : orange red solution.—On addition of hydrochloric acid: red flocks if the solution is strong. —On addition of caustic soda to the aqueous solution: brownish red precipitate.—In conc. sulphuric acid : green solution ; on dilution with water, a blue solution and finally brownish red flocks.—Dyes : wool scarlet from an acid bath. Appearance of dyestuff: brown powder.—In water: magenta red solution.—On addition of hydrochloric acid to aqueous solu- tion : scarcely any change.—On addition of caustic soda: violet * precipitate if the solution is strong,—In conc. sulphuric acid: blue solution ; orange red on dilution with water.—Dyes: wool scarlet from an acid bath. Appearance of dyestuff: bluish black powder.—In water: violet solution.—On addition of hydrochloric acid to the aqueous solution: reddish violet precipitate. —On addition of caustic soda: violet precipitate.—In conc. sulphuric acid: blue solu- tion; on dilution with water, brown precipitate; on boiling, decomposition with formation of tolunaphthazine and amidoazo- benzene-disulphonic acid.—Dyes : wool bluish black from an acid bath. Appearance of dyestuff: brown powder.—In water: magenta red solution.—On addition of caustic soda: solution becomes yel- lower.—On addition of hydrochloric acid: solution becomes reddish violet.—In cone. sulphuric acid: blue solution ; magenta red on dilution.—Dyes: wool archil red from an acid bath. Appearance of dyestuff: reddish brown powder.—In water : scarlet red solution. —On addition of hydrochloric acid: magenta red coloration and precipitate.—On addition of caustic soda to aqueous solution: dirty violet coloration and (if strong) preci- pitate.—In cone. sulphuric acid: blue solution; violet red on dilution.—Dyes : wool red from an acid bath. Appearance of dyestuff: brownish red powder.—In water: red solution.—In alcohol: slightly soluble.—On addition of hydro- chloric acid to the aqueous solution: red precipitate.—On ‘addition of caustic soda: solution becomes violet.—In conc. sulphuric acid: dark blue solution; red precipitate on dilution with water.—Dyes : wool red from an acid bath. Appearance of dyestuff: dark brown powder.—In water or alcohol: red solution.—On addition of hydrochloric acid to the aqueous solution: dark reddish brown precipitate.—On addition of caustic soda: solution slightly browner.—In cone. sulphuric acid: dark green solution; blue solution and then brownish red precipitate on dilution with water.—Dyes: wool red from an acid bath. Appearance of dyestuff: dark green bronzy powder.—In water or alcohol: reddish violet solution.—On addition of hydrochloric acid to the aqueous solution: reddish violet precipitate.—On addition of caustic soda: the solution becomes bluer with sepa- ration of a brownish precipitate.—In conc. sulphuric acid: dull greenish blue solution, on dilution becoming first gray and then giving a reddish violet precipitate.— Dyes: wool from an acid bath or mordanted with chrome, red. * CogHgN,OgS,Nay 14 par — oe bo 144 SS ee ee ee ee ee ee) Commercial Name. Jet Black R. [By.] Fast Violet B. [By.] Diamond Black. [By.] Azonigrine. [G.] Naphthylamine Black D. [¢.] Naphthol Black 6 B. [C.] Brilliant Black B. [B.] Anthracite Black B. [0.] Blue Black B. [B.] Azo Black. [M.] Acid Brown G. [A.] Scientific Name, Empirical Formula. Sodium salt of disulphobenzene-azo- a-naphthalene- azo-phenyl-a- naphthylamine. Sodium salt of sulpho-p-toluene-azo- a-naphthylamine-azo- B-naphthol-p- sulphonie acid. Sodium salt of carboxy-phenol-azo-a- naphthylamine- azo-a-naphthol-p- sulphonic acid. Sodium salt of disulphophenol-azo- a-naphthylamine-azo- B-naphthol. Sodium salt of disulphonaphthalene- azo-a-naphthalene-azo- a-naphthylamine. Sodium salt of disulphonaphthalene- azo-a-naphthalene- azo-8-naphthol- disulphonic acid R. Sodium salt of disulphonaphthalene- azo-a-naphthalene- azo-diphenyl-m- phenylene diamine. Sodium salt of sulpho-8-naphthalene- azo-a-naphthalene- azo-B-naphthol- disulphonie acid. Sodium salt of benzene-azo-phenylene- diamine-azo-benzene- p-sulphonic acid. CypHoN;S,0¢Na, ; : C,H, .N,O;S,Na, C,,H,,N,0;SNa, 16 C59H,)9N,O,5,Na, { 7 YN Copy gN sOr95,Nay C,H o,N,O,S,Na, CypHy,N,0,.93Na, 30 C,,H,,N,0,8Na Constitutional Formula. (SO,Na), 1 oHs\N =N[4]O,,H, [1] N=N[1] C,)Hgl4] NHO,H, C,H, [2] 0H CH, SO Na [6]SO,Na N=N[4]C,,H, [1] N=N [1] CyoHy{ [1]OH OH C,H,4 CO,Na 4]SO,Na N=N [4] CypH,[1]N=N [2] Gg { Ut OH C,H, (80,Na), ' (N=N-[4]C,,H,[1]N=N -[1]C,,)H,[2]0H (SO,Na), Colle SON [4] HyL1IN=N— [1] [4] NE, (S0,Na), [2] 0H N=N[4]C,,H,[1]N =N[1]C,,H,4[3]$0,Na [6]SO,Na C,H, (SO,Na), Cros ae NIAC HIN = N[1]JO,H, ae Ae te [4|NHC HY | SO,Na (2]0H | N=N[4]C,,H,[1] N =N[1]C,,H,4[3]S0,Nal [6]SO,Na Ci pH, Cae | 4 = Method of Preparation. Diazo Compound from Disulpho- benzene-azo- a-naphthyl- amine, Sulpho-p- toluene-azo-a- naphthylamine. Salicylic-acid- azo-a-naphthyl- amine. Disulpho- phenol-azo-a- naphthylamine. Disulpho- naphthalene- azo-a-naphthyl- amine. Disulpho- naphthalene- azo-a-naphthyl- amine. Disulpho- naphthalene- azo-a-naphthyl- amine, * Mono- (or di-) sulpho-f- naphthalene- azo-a-naphthyl- amine. Aniline. Combined with Phenyl-a- naphthylamine. 8-Naphthol- B-sulphonic acid. a-Naphthol- monosulphonic acid NW. 6-Naphthol. a-Naphthyl- amine. 8-Naphthol- disulphonic acid R. Diphenyl-m- phenylene- diamine. B-Naphthol- disulphonic acid R. Diamidoazo- benzene-p- sulphonic acid (from sulphanil- ic acid and | m-phenylene- diamine), Year of Discovery. 1888. 1882. 1886. 1889. Discoverer. Patents. Literature. M. Kaun. Fr. BAYER & Co. Eng. Pat. 1444258, Am. Pat. 425885. Ger. Pat. 4892488, J. Soc. Dyers and Colorists, 1889, 106. Fr. BAYER & Co. . L. CAssELLA & Co. Ger. Pat. 40977%. Behaviour with Reagents. Shade and Dyeing Properties, Method of Employment. Appearance of dyestuff: black powder.—In water: bluish violet solution.—In alcohol: violet solution.—On addition of hydro- chloric acid to the aqueous solution: bluish black precipitate. —On addition of caustic soda to the aqueous solution : soluble violet precipitate.—In conc. sulphuric acid: blue solution; greenish blue precipitate on dilution with water.— Dyes: wool bluish black from an acetic acid bath or a neutral bath containing salt. Appearance of dyestuff: greenish brown powder.—In water or alcohol: violet solution.—On addition of hydrochloric acid to the aqueous solution: violet precipitate.—On addition of caustic soda to the aqueous solution: violet precipitate if the solution is strong—In conc. sulphuric acid: dull green solution ; violet precipitate on dilution.—Dyes: wool violet from an acid bath. R. Laucne & K. KRexkeuer. Fr. Bayrr & Co. Eng. Pat, 8299°®. Am. Pat. 488488. Ger. Pat. 5150499. 1391; 1888. 1885. 1889. 1882. 1882. T. SANDMEYER. J. R. Griey & Co. Eng. Pat. 17711°. Fr. Pat. 2167809. A, WEINBERG. L. CAssELLA & Co. Eng. Pat. 18425%8, Am. Pat. 412440, Ger. Pat. 50907 ; addn. to 39029, M. HorrmMann & A. WEIN- “BERG. L. CASSELLA & Co. Ing. Pat. 9214®° (amended). Am. Pat. 345901. Ger. Pat. 39029. Rib atach 05425 L. CAssELLA & Co. Eng. Pat. 7977. Employment : J. Soc. Chem. Ind, 1892, 31. Bap. Antn. & Sopa FABRIK. L. LIMPACH. MaistTErR, Lucius, & BrUNING. Appearance of dyestuff: blackish blue powder.—In water or alcohol: bluish violet solution.—On addition of hydrochloric acid to the aqueous solution: violet precipitate.—On addition of caustic soda: solution becomes blue.—In conc. sulphuric acid: greenish solution ; violet precipitate on dilution with water. —Dyes: chrome mordanted wool bluish black, the shades being very fast to light, milling, stoving, acids, and alkalies. Appearance of dyestuff : brownish black powder.—In water : bluish black solution.—On addition of hydrochloric acid to the aqueous solution: becomes red.—On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid : greenish black solution; red precipitate on dilution with water. —Dyes: wool brownish black. Appearance of dyestuff: black powder.—In water: violet black solution.—In alcohol: insoluble-—On addition of hydrochloric acid to the aqueous solution; black precipitate.—On addition of caustic soda: no change.—In conc. sulphuric acid: bluish black solution; on dilution with water, first green, then a black precipitate. —Dyes: wool and silk black from an acid bath or from a neutral bath containing salt. Appearance of dyestuff: black powder.—In water : easily soluble with a violet colour.—In alcohol: insoluble.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda to the aqueous solution: blackish blue colour.—In conc. sulphuric acid: greenish black solution ; on dilution with water, first greenish blue, then a violet precipi- tate.—Dyes : wool bluish black from an acid bath. Appearance of dyestuff: blackish powder.—In water: dull violet solution. —On addition of hydrochloric acid to the aqueous solution: violet precipitate.—On addition of caustic soda: no change.—In cone, sulphuric acid : black solution ; greenish black precipitate on dilution.—Dyes: wool from an acid bath a black fast to milling. Appearance of dyestuff: bluish black powder.—In water: bluish violet solution. —On addition of hydrochloric acid to the aqueous solution: blue precipitate. —On addition of caustic soda to the aqueous solution : blue precipitate, soluble in water. —In conc. sulphuric acid: bluish green solution; on dilution with water, blue solution and then a blue precipitate. —Dyes: wool bluish violet from an acid bath. 1882. ACTIENGESELLSCH¢ F, ANIL. FABRIKN. Ger. Pat. 22714°. Chem, Ind, (1883) 6, 207. Appearance of dyestuff: brown powder.—In water: brown solu- tion.—On addition of hydrochloric acid to the aqueous solu- tion : no change.—On addition of caustic soda: no change.—In cone. sulphuric acid: reddish brown solution ; yellowish brown on dilution.—Dyes: wool brown from an acid bath. -isemployed. For Azo Black the mixture of mono- and di-sulphonic acids obtained by sulphonating B-naphthylamine is used. ie Hee ea an {Cae 6 Constitutional Formula. (jon ~[2]C,H, 22108 [4]N =N -[1]C,H,[4]80,Na ae (4 SO,Na No.| Commercial Name. Scientific Name. Empirical Formula. 146} Resorcin Brown. Sodium salt of Cy9H,,N,0,5Na [A.] xylene-azo-resorcin- ; azo-benzene- p-sulphonic acid, 147| Fast Brown G. Sodium salt of C,H iN ,O,5,Nas [A.][Z. M.] bi-sulphobenzene- , * i ie Se disazo-a-naphthol, 148 Fast Brown. Sodium salt of CygHgN ,0.8,Na, [By.] bisulphonaphthalene- Pets : disazo-resorcinol. 149| Bismarck Brown. | Hydrochloride of Ciba NCL, Manchester benzene-disazo- Nees phenylene-diamine. Phenylene Brown. Vesuvine. Leather Brown. Cinnamon Brown. English Brown. 150| Leather Brown. [0.] 151| Toluylene Brown. Sodium salt of CygHogN 50 ,S,Na, [0] sulphotoluene-disazo- She ate leg ; phenylene-diamine- bi-azo-naphthionic acid. 152|Manchester Brown} Hydrochloride ORS ACEO) BE. [C1] of toluene-disazo-m- 3 tolylene-diamine. 153 Clayton Sodium salt Cy3H,.N,O,S,Na, Wool Brown of benzene-sulpho- 3 z Cl. Cl i benzene-sulpho- [Cl. Co.] naphthalene-trisazo- m-phenylene-diamine. 154| Violet Black. Sodium salt of C,,H,.N,0,SNa [B.] a-naphthylamine-azo- benzene-azo-a- naphthol-y-sulphonic acid. “FN =N[2] oa (HIN NL \c, H,(1]0H £\[4]SO,Na [4]S0,Na CoH ]N=N No, 11,{(1] 0H oH {LIN=N 4° 203] 08 1046 F4]$0,Na [1JN=N-[1] C,H, A Net CoH, a NH,HCI [3]N=N-[1] CHe{t a]NHC N = N ~ G,Hy(SH - N=N ~ CygHly- SO,Na CoH) S0,Na N=N-0,H,(NH,), - N=N -C,,H,-S0,Na - [2] NH, HCl [3]N=N[1] C,H, "I mee boheee [2] NH,HCl [1]N =N[1]0,H,1 [4] NH, [5] CH, OH, N= Nv 1] NH C,H,(SO,Na) — > o,n{f 2 C,,H,(S0,Na) — None © Na [1]0H te N=N-[1]C,,H,[4] NH, CH “12 Oyo {F 4 SO,Na [4JN=N Method of Preparation. Discoverer. Literature. O. WALLACH. ACTIENGESELLSCH, F. ANIL. FABRIKN. Am. Pat. 269359. Ger. Pat. 188618). Patents. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. C. Krouy. Ber. (1888) 21, 3241. Appearance of dyestuff: brown powder.—In water: brown solu- tion.—On addition of hydrochloric acid to the aqueous solu- tion : brown precipitate. —On addition of caustic soda to the aqueous solution: scarcely any change.—In conc. sulphuric acid: brown solution ; brown precipitate on dilution with water. —Dyes: wool brown from an acid bath. Appearance of dyestuff: brown powder.—In water : reddish brown solution.—On addition of hydrochloric acid to aqueous solu- tion: violet precipitate.—On addition of caustic soda to aqueous solution: cherry red colour.—In conc. sulphuric acid: violet solution ; yellowish brown on dilution.—Dyes: wool brown from an acid bath. ACTIENGESELLSCH. F. ANIL. FABRIKN. Ger. Pat. 18861 (lapsed). Dyes: wool brown from an acid bath. Year of Diazo Compound | Combined with EESOSEEY Xylidine. p-Sulpho- 1881, benzene-azo- resorcinol (Tropeoline 0). 2 mols. of 1 mol. of 1882. sulphanilic a-naphthol. acid. 2 mols. of 1 mol. 1881. | naphthionic resorcinol. acid, 1 mol. of 2 mols. of 1863. m-phenylene- | m-phenylene- diamine, — diamine. ; | Combination of 2 mols. of 1890. p-diazo-acetanilide with 1 mol. of m-phenylene-diamine and heating the product with cone. hydrochloric acid. 1 mol. of 2 mols. of 1889. m-tolylene- | m-phenylene- diamine-sul- diamine. phonic acid and 2 mols. of > naphthionic acid. 1 mol. of 2 mols. of 1878. m-tolylene- m-tolylene- diamine. diamine. 6 mol. of 1 mol. of 1891. | aniline, 1 mol. | m-phenylene- | of sulphanilic diamine. acid, andl mol.| . of naphthionic acid. Combination of diazo- 1887. acetanilide with a-naphthol- monosulphonic acid NW., | splitting off the acetyl group, | diazotising the obtained base, | and combination with a- naphthylamine. MARTIUS. DALE & CARO. Eng. Pat. 3307%, Caro & P. Grizss. Zeit. f. Chem, (1867) 3, 287. Cur. RupotpH & G. PALM. K, OEHLER. Ger. Pat. 57429%. Appearance of dyestuff: dark brown powder.—In water: brown solution.—On addition of hydrochloric acid to the aqueous solu- tion : no change.—On addition of caustic soda to the aqueous solution: brown precipitate.—In conc. sulphuric acid: brown solution; red on dilution with water.—Dyes: wool, leather, and tannined cotton reddish brown, Appearance of dyestutf: blackish powder.—In water: brown solution.—On addition of hydrochloric acid: the solution becomes yellower.—On addition of caustic soda: brown preci- pitate. —In conc. sulphuric acid: brown solution: yellowish brown on dilution.—Dyes : leather and jute brown. Cur. RupotpH & E. VoGEs. K. OfHLER. Ger. Pat. 58657®. P. GRizss. Ber. (1878) 11, 627. de Jebatin, THE CLAYTON ANILINE Co. Eng. Pat. 15494%, Bap. ANIL. & SopA FABRIK. Ger. Pat. 428148”, addn. to 42011°7, Appearance of dyestuff: brownish black powder.—In water: brown solution.—In alcohol: almost insoluble.—On addition of hydrochloric acid to the aqueous solution : brown precipitate. —In cone. sulphuric acid: dull violet colour; brown solution on dilution with water.—Dyes : cotton brown from an alkaline bath. Appearance of dyestuff: dark brown powder.—In water: reddish brown solution.—In alcohol: reddish brown solution.—On addi- tion of hydrochloric acid to the aqueous solution: yellowish brown colour.—On addition of caustic soda: light brown pre- cipitate.—In conc. sulphuric acid: dark brown solution; on dilution becoming red and then brown.—Dyes : wool, leather, and tannin mordanted cotton reddish brown. Appearance of dyestuff: brown powder.—In water: soluble with a brown colour.—Dilute acids or alkalies: no change.—Dyes: wool or silk brown. Appearance of dyestuff: bronzy powder.—In water: brownish red solution. —On addition of hydrochloric acid to the aqueous solution: violet precipitate.—Dilute acetic acid: solution be- comes reddish violet. —On addition of caustic soda: solution becomes reddish violet.—In conc. sulphuric acid: blue solution ; violet precipitate on dilution with water.—Dyes : cotton and wool violet black. : No.| Commercial Name. Scientific Name. Sodium salt of azoxytoluene-disazo- bi-a-naphthol- sulphonic acid. ae, a Empirical Formula. Cy4HogN (0 9S,Na, Sodium salt of phenyl-dixylyl- methane-disazo-bi-B- naphthol- disulphonic acid. 155| St. Denis Red. [P.J[4] 156| Cotton Scarlet. [B. KJ 157 Salmon Red. [B.] 158 | Cotton Yellow G. [B.] [B] 160| Diamine Gold. [C.] 161| Stilbene Red.* [A.] 162| Brilliant Yellow. [Z.] [A.] [By-] 163| Polychromine B. [G.] 159| Naphthylene Red. Sodium salt of diphenylurea-disazo- bi-naphthioniec acid. Sodium salt of diphenylurea-disazo- bi-salicylic acid. Sodium salt of naphthalene-disazo- bi-naphthionie acid. Sodium salt of disulphonaphthalene- disazo-bi-phenetol. Sodium salt of stilbene-disazo- B-naphthylamine- a-naphthylamine- trisulphonie acid, Sodium salt of disulpho-stilbene- disazo-bi-phenol. Sodium salt of disulpho-stilbene- disazo-bi-aniline. C,H N40) ,8,Na, C,5H,,N,0,8,Na, C,H, N,O,Na, CypHooN gOgS.Na, C,gHy9N,0,8,Na, C,H, ,N,0.5,Na, CgHygN,O,S,Na, C. 3H. N,0,8,Na, 26 Constitutional Formula. N — C,H,(CH,) - N=N - C,,H,(OH)SO,Na 0< | N — C,H,(CH,) - N=N — C,,H,(OH)SO,Na C,H,(CH,), - N=N — 0,,H,(OH)(S0,Na), cu C,H, C,H,(CH,), - N=N — C,,H,(OH)(S0,Na), [1] NH, NH.O,H,-N=N- Cys Fa 830,Na 00 1) NH, NH. 0,H,-N=N- OyeH sft pe 50.416 [1]OH NH. O,H,-N=N- Cvs co, Na 00 NH -C,H,-N=N- CsH{ a4 ]OH 2]CO,Na [1] NH, [4]80,Na” 1]NH, ale SO,Na (1 Ne CoH, { "BIN=NEI1C, [1JN=N[1]C,H,[4]00,H, [5]N=N [1] C,H, [4] 00,4, [2] NH, (S0,Na), [1] NH, 4]SO, Na CH[1] C,H [4]-N=N-[1] oH,{ CH[1]0,H,[4]- N=N -[2]0,,H, AN [2]SO,Na [4]N=N[1]0, H [40H [4]N= N[1] 6, H, 44] OH [2] SO,Na CH[1]C,H, CHI] CyHa{ [2] SO,Na [4] N=N -[1] C,H, [4] NH, [4] N=N — [1] Oj, [4] NH, [2]SO,Na CH [1] GyHy{ CH [1] C,H, * Stilbene Red G [4.] is formed by ae ae ee a ee ee ee a ae ete [omer | Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Diazo see cea Becabiaad with Discovery. Literature. Method of Employment. 1 mol. of 2 mols. of 1887. Noxirina & RosENSsTIEHL. | Appearance of dyestuff: red powder.—In water: red solution.—In diamidoazoxy- | a-naphthol- Soc. Anom. des Mat. Color. alcohol: slightly soluble.-—On addition of hydrochloric acid to toluene. monosulphonic et Produits Chemiques. the aqueous solution: red precipitate.—On addition of caustic acid NW. Ger. Pat. 4404587, soda to the aqueous solution : brick red precipitate.—In conc. 4 Eng. Pats. 93158? and 5736”, sulphuric acid : red solution ; red precipitate on dilution.—Dyes : Farberzeitung, 1, 106. cotton red from an alkaline bath. 1 mol. of 2 mols. of 1887. HoFFMANN. Appearance of dyestuff: reddish brown powder.—In water: red diamido-di- B-naphthol- LereziceR ANIL. FABRIK solution.—In alcohol: insoluble.—On addition of hydrochloric xylyl-phenyl- disulphonic Bryer & KEGEL. acid to the aqueous solution: no change.—On addition of methane. acid R. Ger. Pat. 4364487 (lapsed). caustic soda: solution becomes a deeper red.—In conc. sulphuric acid : brownish red solution ; yellowish red on dilution with water. —Dyes: unmordanted cotton red from a boiling alkaline bath. Combination of diazotised 1888. CG. L. MUuuer. Appearance of dyestuff: brownish powder.—In water: orange p-amidoacetanilide with naph- Bap. ANIL. & SopA yellow solution.—On addition of hydrochloric acid: bluish | thionic acid, saponification of FABRIK. violet precipitate.—On addition of caustic soda: no change.— the product, and treatment Eng. Pat. 1422289, In conc. sulphuric acid: magenta red solution; bluish violet with carbonyl chloride. Am. Pat. 4305342, precipitate on dilution with water.—Dyes: unmordanted cotton Ger. Pat. 5085229, from a boiling alkaline bath shades ranging from flesh colour to brownish orange. ‘Combination of diazotised 1888. C. L. MULuEr. Appearance of dyestuff: yellowish powder.—In water: yellow p-amidoacetanilide with sali- BAp. ANIL. & SoDA solution. —On addition of hydrochloric acid to the aqueous _ | eylie acid, saponification of the FABRIK. solution: brown precipitate. —On addition of caustic soda: | product and treatment with Eng. Pat. 15258°8, solution becomes rather more orange.—In conc. sulphuric acid: : carbonyl chloride. Am. Pat. 430535, orange red solution; bluish violet precipitate on dilution with Ger. Pats. 467378 and water.—Dyes: unmordanted cotton yellow from a boiling alkaline 4790289, bath. J. Soc. Dyers and Colorists, 1889, 106. ‘ al mol. of 2 mols. of 1886. A. ROMER. Appearance of dyestuff: brownish red powder.—In water: red | (1:5)-diamido-| naphthionic Bap. ANIL. & SODA solution. —On addition of hydrochloric acid to the aqueous _ | naphthalene. acid. FABRIK. solution: violet black precipitate.—On addition of caustic soda n Eng. Pat. 14625%, to the aqueous solution: no change.—In conc. sulphuric acid : % Am. Pat. 3595768, blue solution; bluish black precipitate on dilution with water.— - Ger. Pat. 3995486, Dyes: unmordanted cotton red from a boiling alkaline bath. 7. aoe 3 2 1 mol, of 2 mols. of 1890. M. HorFrMAnn. Appearance of dyestuff: bright orange yellow powder.—In water : fle bis 3 3.7.) phenol. L. CAssettA & Co. insoluble in cold, yellow solution in hot.—In alcohol: yellow | diamido-naph- Eng. Pat. 15346, solution. —On addition of hydrochloric acid to the aqueous thalene-disul- solution: brownish yellow precipitate, turned black by a large phonic acid, excess.—On addition of caustic soda: gelatinous yellow preci- Li : pitate.—In conc. sulphuric acid: reddish violet solution; on And ethylating the product. dilution dull green and then yellow.—Dyes : unmordanted cotton yellow. i mol. of 1 mol. of 1888. G. ScHULTz. Appearance of dyestuff: reddish brown powder.—In water: red | pp-diamido- B-naphthyl- AOTIENGESELLSOH. F. ANIL. solution.—In alcohol: slightly soluble.—On addition of hydro- stilbene. amine-disul- FABRIKN. chloric acid to the aqueous solution : blue black precipitate.— | phonic acid, Eng. Pat. 728486 (amended). On addition of caustic soda: no change.—In cone. sulphuric | and 1 mol. of Ger. Pat. 47026%, third acid: blue solution; reddish black precipitate on dilution with | naphthionic addn. to 397568, water.—Dyes : unmordanted cotton red from a salt bath. | acid. ee ee —EeE——EE 1 mol. of 2 mols. of 1886. F. BENDER. Appearance of dyestuff: light brown powder.—In water : reddish diamido- phenol. A. LEONHARDT & Co. yellow solution. —On addition of hydrochloric acid to the | stilbene-disul- Eng. Pat. 438756, aqueous solution: violet precipitate. —On addition of caustic | phonic acid. Am. Pat. 350229. soda to the aqueous solution: yellowish red colour.—In cone. 7 Ger, Pat. 38735%. sulphuric acid: reddish violet solution; violet precipitate on 4 dilution with water.—Dyes: unmordanted cotton yellow from a soap bath. ‘ ‘Boiling equal mols. of p-nitro- 1890. Cu. Ris. Appearance of dyestuff: reddish brown powder.—In water: | toluene-sulphonic acid and J. R. Getey & Co. orange brown solution,—On addition of hydrochloric acid to p-phenylene-diamine with Eng. Pat. 15671. the aqueous solution: blue black precipitate.—On addition of aqueous caustic soda. Am. Pat. 45595291, caustic soda : no change.—In conc. sulphuric acid : reddish violet Ger. Pat. 59290%. solution ; bluish black precipitate on dilution with water.—Dyes : Fr. Pat. 208626. unmordanted cotton orange brown from a neutral or alkaline bath. Yields various shades of ‘“‘ingrain” brown by diazotisation upon the fibre and “development” with phenylene diamine, ete. Loe oa No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula, 164} Chrysophenine. Sodium salt of Cz ,HogN,0,8,Na, [2] SO.Na [L(A] [By] | gee hotel CH — [1] CcHs\ [4] N = N — [4] C,H, [1] 0C,H, CB it G-H. [4] N=N —[4] C,H, [1] OC_H; 63 [2] SO,Na 165 [Hessian Purple N. Sodium salt of Cy,HoN,OSaN a, ae [2]SO,Na [iz] [4] [Bu eal cee pages en te | UIN=N~[1] Cull [2] NB Aho CH Stier [4] N=N —[1] C,H, [2] NH, [1] CoH) [2] $0,Na 166| Brilliant Hessian : Rodi ae Ga CygHygN g0,8,Na, | cy _ [1] OH, [2] SO,Na [2] NH, : Purple. elas [4] N=N —[1] C,H, | [E.] [4] [By] disazo-bi-8-naphthyl- | 5) (6) 30. Na RAS eRe CH CH [4] N=N—[1] C,)H, 7] a N. | ~ 011 %cHs) (9) 30,Na iG] 80am 167 | Hessian Purple B. Sodium salt of C,,H, N .0,.5,Na, Ci [2] SO.Na ’ disulpho-stilbene- H —[1] C,H, Sa [2] NH, [L.] [4.] [By.] disazo-i-f-naphthyl | [4] N=WN [1] C,H; ee amine-suiphonic acid. Seite 2 ore CoM 168| Hessian Purple D,| _ Sodium salt of CypHooNg01.8,Na, } cy [2] SO,Na disulpho-stilbene- -[1] CH{ ee [2] NH, LE TA Eee isan tena phtly!s L4IN=N—[1] Ciolts SO0,Na amine-sulphonic acid. c [2] NH, CH -[1] oH { tI s0.Ne ~ FI Cols | s6,Na 169| Hessian Yellow. Sodium salt of C,.H, .N,0,,5,Na, " [2] SO,Na (L]L41 [By] | lisuphostiien FUSE (ic 1]0H Ks [4] N=N-C,H, CH [1] CoHs{ 12] $0,Na [2] CO,H 170| Hessian Violet. Sodium salt of Cz,HogN,0,8,Na, [2] SO,Na [L.] [4.] [By] disulpho-stilbene- CH — [1] C,H, [4] N=N-[4]C,,H, [1] NH disazo-a-naphthyl- I rm 6 HW amine-B-naphthol. CH — [1] 0,H, 2 ae es — [1] C,H, [2] 0 3 171| Sulphanil Yellow.| Sodium salt of | G,,H..N,O,8,Na C,H, [4] -N=N - NH [4] C,H, [1] S0,Na Parasulphurine §.) 0m | CL ee [B. K] aad, C,H, [4] - N=N —- NH [4] C,H, [1] SO,Na 172| Congo Yellow in Sodium salt of C,,H,.N,0,SNa C,H, [4] -N=N — NH [4] C,H, [1] SO,Na paste. [4.][By.] | _ diphenyl-disazo- [1] Siaivied seecainating C,H, [4] - N=N - [4] ©,H, [1] 0H a) Method of Preparation. Am. Pats. 160722 & 163172. Ger. Pat. 40954%6, Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Diazo Sompound Be ea ind wits Discovery. Literature. Method of Employment. Ethylation of “Brilliant Yellow” 1886. F, BENDER. Appearance of dyestuff: orange yellow powder.—In water: spar- (No. 162). A. LEoNHARDT & Co. ingly soluble cold, easily hot, with an orange yellow colour.—On Eng. Pat. 42.4386, addition of hydrochloric acid to the hot aqueous solution: Am. Pat. 379487. brown precipitate.—Dilute acetic acid: scarcely any change.— Ger. Pat. 42466 ; second On addition of caustic soda to the hot aqueous solution: yel- addn. to 3873585, low coloration and orange flocks.—In conc. sulphuric acid: reddish violet solution; blue precipitate on dilution.—Dyes: un- mordanted cotton yellow from a soap bath. 1 mol. of 2 mols. of 1886. F. BenpDER. Appearance of dyestuff: brownish red powder.—In water: cherry diamido- $-naphthy]l- A. LRoNHARDT & Co. red solution.—On addition of hydrochloric acid to the aqueous stilbene-disul- amine. Eng. Pat. 438786 (amended). solution: bluish black precipitate.—Dilute acetic acid: violet phonic acid. Am. Pat. 350230. black precipitate.—On addition of caustic soda to the aqueous Ger. Pat. 38735%% solution: red coloration and red precipitate.—In conc. sulphuric acid: blue solution; bluish black precipitate on dilution with water.—Dyes: unmordanted cotton bluish red from a soap bath. 1 mol. of 2 mols. of 1886. F. BENDER. Appearance of dyestuff: dark red powder.—In water: purple red diamido- B-naphthyl- A. Lronnarpt & Co. solution.—In alcohol: slightly soluble.-—On addition of hydro- stilbene-disul- | amine-mono- Eng. Pat. 43878° (amended). chloric acid to the aqueous solution: bluish black precipitate. phonic acid. | sulphonic acid Am. Pat. 350230. —On addition of caustic soda to the aqueous solution: car- " Ger. Pat. 38735%%, mine red precipitate.—In conc. sulphuric avid: blue solution ; bluish black precipitate on dilution with water.—Dyes : unmor- danted cotton bluish red. 1 mol. of di- 2 mols. of B- 1886. F, BENDER. Appearance of dyestuff: brown powder.—In water: cherry red amido-stilbene- naphthylamine A. LEonHARDT & Co. solution. —On addition of hydrochloric acid to the aqueous disulphonic sulphonic acid Eng. Pat. 4387% (amended). solution: brownish black precipitate.—Dilute acetic acid: solu- acid. B (or a mixture Am. Pat. 250230. tion becomes darker.—On addition of caustic soda to the of 6 and 6). Ger. Pats. 3873586 & 4057585, aqueous solution : reddish violet precipitate, soluble in water.— In conc. sulphuric acid: violet solution; brown precipitate on j dilution with water.—Dyes ; unmordanted cotton bluish red from a soap bath. 1 mol. of di- 2 mols. of B- 1886. F, BENDER. Appearance of dyestuff: black powder.—In water: orange red amido-stilbene | naphthylamine A. LEonHARDT & Co. solution.—On addition of hydrochloric acid to the aqueous disulphonic | monosulphonic Eng. Pat. 43878 (amended). solution: brown precipitate.—Dilute acetic acid: no change.— acid. acid +. Am. Pat. 350230. On addition of caustic soda to the aqueous solution: bluer.— Ger. Pat. 38735%8, In conc. sulphuric acid: violet solution ; brown on dilution with water.—Dyes: unmordanted cotton bluish red from a soap bath. 1 mol. of di- 2 mols. of 1886. F. BENDER. Appearance of dyestuff: ochre yellow powder.—In water: brown- amido-stilbene salicylic acid. A. LEoNHARDT & Co. ish yellow solution.—On addition of hydrochloric acid to the disulphonic Eng. Pat. 4387% (amended), aqueous solution: blackish precipitate.— Dilute acetic acid: acid. Am. Pat. 350229. searcely any change.—On addition of caustic soda to the Ger. Pat. 38735. aqueous solution: cherry red coloration.—In conc. sulphuric acid: reddish violet solution; blackish precipitate on dilution with water.—Dyes: unmordanted cotton yellow from a soap bath. 1 mol. of di- 1 mol. of a- 1886, I F. BENDER. Appearance of dyestuff: black powder.—In water: reddish violet amido-stilbene naphthylamine A. LmronHARDT & Co. solution.— On addition of hydrochloric acid to the aqueous disulphonic and 1 mol. of Eng. Pat. 4387 (amended). solution: blue precipitate.—Dilute acetic acid : solution becomes acid. B-naphthol, Ger. Pats. 387358 & 4057586, bluish violet.—On addition of caustic soda: solution becomes bluish violet—In conc. sulphuric acid: blue solution ; violet pre- cipitate on dilution with water.—Dyes: unmordanted cotton violet from a soap bath. 1 mol. of 2 mols. of 1884, C. DUISBERG. Appearance of dyestuff: brownish yellow paste or powder.—In benzidine. _|sulphanilic acid. Fr. Bayer & Co. : water : greenish yellow solution.—Dilute acetic acid : no change. Ger. Pat. 3295884, On addition of caustic soda to the aqueous solution: no change.—On heating with acids: decomposition with evolution of nitrogen.—Dyes: unmordanted cotton greenish yellow from a soap bath. 1 mol. of 1 mol. of 1885. S, Prarr. Appearance of dyestuff: brownish yellow paste.—In water: yel- benzidine. | sulphanilic acid ACTIENGESELLSCH. F. ANIL, | —_Jow solution.—On addition of hydrochloric acid to the aqueous and 1 mol. of FABRIKN. solution: brown precipitate,—Dilute acetic acid: brown preci- phenol. Eng. Pat. 2213°* (amended). pitate.-—On addition of caustic soda: solution becomes yellow- ish brown.—In conc. sulphuric acid: brownish red solution ; brown precipitate on dilution.—Dyes: unmordanted cotton yellow from a soap bath. [ 100 ] No.| Commercial Name. Scientific Name. 173} Azoorseilline. be So a a é Wi ipheny]-disazo-bi- bac 2, a-naphthol-p- sulphonic acid. 174 Congo Violet. Sodium salt of [A] dipheny1-disazo-bi- B-naphthol-p- comes cov. sulphonic acid. Bordeaux Extra. [Py.] Empirical Formula, Constitutional Formula. CypHopN,0,8,Na, CypHopN ,Os8)Nay 175| Congo Corinth G. Sodium salt of CoH, N;0;S,Nay CogHyoN gO5S,Nay 1) | O,H, [4]-N=N- [2] C,H, ee Hae C,H, [4]-N=N- C,H, [4]-N=N- C,H, [4])-N=N- C,H, [4]-N=N- C,H, [4] -N=N- [1] | C,H, [4] - [2] CioHs fa 50, Na [4] SO,Na [2] CoH Fr} OH [1] CioH, ey 50, Na 1] CoH Fay S0,Na [2] CoH, (ce SO, se [4] SO,Na CH fry Hh C,H, [4] - N=N - NH [1] C,H, [3] SO,Na CysH)N,0,8)Na, dipheny]-disazo- [4.1 (By. naphthionic-a- naphthol-sulphonic acid. 176 Congo G. Sodium salt of dipheny]-disazo- [4] [By-] naphthionic-m-amido- benzene-sulphonic acid, 177 Congo Red. Sodium salt of [A.] [By] dipheny]-disazo-bi- naphthionie acid. Sodium salt of 178 | Deltapurpurine G. [By.] diphenyl-disazo-bi-A- (No longer in com- naphthylamine- tebe sulphonic acid. Sodium salt of dipheny]-disazo-B- naphthylamine- sulphonic-f- naphthylamine- disulphonic acid. 179| Brilliant Congo G. [A.] [By.] Chrysamine G. Sodium salt of dipheny]-disazo-bi- Bee salicylic acid. [B.] Cz9HoN ,OgS.Na, CypH NgO8,Na, C,H, gN,O,Na, * The dyestuff also contains the compounds from 1 mol. benzidine and 2 mols. of + Gladioline O and Gladioline I are mixed tetrazo dyestuffs derived from benzidine and @-naphthylamine-sulphonie acid B. to contain oreinol, ep. Am. Pat. C,H, [4] -N=N- CoH, [4] - C,H, [4]-N=N- C,H, (4) -N=N- C,H, [4] -N=N- nih C,H, [4)-N=N- C,H, [4] -N=N- [1] | C,H, [4]-N=N- 4]SO Na [1] NH, [2] CoH ae S0,Na “aoa, (1) CroHs{ fe] Soe [1] ole (3480, Na [1] CoH, a S08 Na [6]SO,Na [1] cyt S0,Na [2] NH, 1] 0H [4] CHa ay CO,H LICH ion Perot + Method of Preparation. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: dark violet paste-——In water: reddish violet solution.—On addition of hydrochloric acid to the aqueous solution: violet precipitate.—Dilute acetic acid: no change.—On addition of caustic soda: solution becomes cherry red,—In cone. sulphuric acid: blue solution; violet precipitate on dilution with water.—Dyes: cotton brownish red from a soap bath. Appearance of dyestuff: brown powder.—In water: bordeaux red solution. —On addition of hydrochloric acid to the aqueous solution: violet precipitate.—Dilute acetic acid: no change.— On addition of caustic soda: solution becomes yellower.—In conc. sulphuric acid: violet solution; violet precipitate on dilution with water.—Dyes : wool bordeaux red from an acid bath ; cotton violet from a salt bath. — Appearance of dyestuff: greenish black powder.—In water: ma- genta red solution.—On addition of hydrochloric acid to the aqueous solution : violet precipitate.—Dilute acetic acid: solu- tion becomes violet.—On addition of caustic soda: solution becomes cherry red.—In conc. sulphuric acid: blue solution; violet precipitate on dilution with water.—Dyes: cotton brownish violet from a soap bath. Appearance of dyestuff: brown powder.—In water: brownish red solution.—On addition of hydrochloric acid to aqueous solu- tion: blue precipitate.— Dilute acetic acid: violet precipitate. On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: blue solution; blue precipi- tate on dilution with water.—Dyes: cotton red from a soap bath. Appearance of dyestuff: reddish brown powder—In water: red- dish brown solution.—On addition of hydrochloric acid to the aqueous solution: blue precipitate.—Dilute acetic acid: bluish violet precipitate.—On addition of caustic soda to the aqueous solution : reddish brown precipitate, soluble in water.—In conc. sulphuric acid: blue solution; blue precipitate on dilution.— Dyes: wool or unmordanted cotton red from a neutral or alkaline bath. Appearance of dyestuff: brownish red powder.—In water: spar- ingly soluble cold, with orange red colour hot.—On addition of hydrochloric acid to the aqueous solution: deep brown preci- pitate.— Dilute acetic acid: brownish red precipitate. —On addition of caustic soda to the aqueous solution : no change. —In conc. sulphuric acid: blue; brown precipitate on dilution with water.—Dyes: unmordanted cotton red from a soap bath. Year of Discoverer. Patents. 1 mol. of 2 mols. of 1883, O. N. Wirt. : benzidine. a-naphthol- VEREIN CHEM. FABRIKEN. | monosulphonic Eng. Pats, 223783 & 423783, acid NW. Ger. Pat. 2601283, 1 mol. of 2 mols. of 1883. G. ScHuLrz. benzidine. B-naphthol- Ber. (1884) 17, 462. sulphonic acid 1884. Ki. FRANK. Fr. Bayer & Co. Eng. Pats. 1225°! and 8495%. Ger. Pat. 300778 ; fourth addn. to 18027. 1 mol. of 1 mol. of 1886, S. PFAFF. benzidine. naphthionic ACTIENGESELLSCH. F. A NIL. acid and 1 mol. FABRIKN. of a-naphthol- Eng. Pats. 15296, 2213°6, monosulphonic 6687%° acid NW. Am. Pat. 344971. Ger. Pat. 89096% ; second : addn. to 29753. 1 mol. of 1 mol. of 1885 S. PFAFF. benzidine. m-sulphanilic ACTIENGESELLSCH. F. ANIL. | acid and 1 mol. FABRIEN. : of naphthionic Eng. Pats. 152968 & 2213 acid. (amended). 5 Am, Pats. 160722 & 163172. : Ger. Pat. 40954°°, | ; 4 1 mol. 2 mols. 1884. P. BOTTINGER. : benzidine. naphthionic Eng. Pat. 4415%* (amended). : acid. Ger. Pat; 2875384 : O. N. Wirt. Ber, (1886) 19, 1719. : : 4 1 mol. 1 mol. each p- 1886. |Fr. Bayer & C. DuisBErc. benzidine. naphthylamine Ber. (1887) 20, 1430. monosulphonic Fr. BAYER & Co. acid B and ee Eng. Pats 584688, Ger. Pat. 42021°, dependent on 28753, 1 mol. 1 mol. each B-| 1886. S. PrAFF. benzidine, | naphthylamine R. KricEner. monosulphonic ACTIENGESELLSCH. F. ANIL. acid B and di- FABRIKN. sulphonic acid Eng. Pat. 6687” (amended). Ret Ger. Pat. 41095® ; third addn. to 28753. 1 mol. 2 mols, 1884. E. FRANK, benzidine, salicylic acid. Fr. Bayer & Co. Eng. Pat. 916254, Am. Pat. 329638. Ger. Pat. 316584. 8-acid, and from 1 mol. benzidine and two mols. of-5-acid ; cp. Ber. (1887) 20, 3160. Appearance of dyestuff: brown powder.—In water: brownish red solution.—On addition of hydrochloric acid to the aqueous solution: brownish violet precipitate.—Dilute acetic acid : solu- tion rather bluer.—On addition of caustic soda to the aqueous solution : little change.—In conc. sulphuric acid: blue solution ; violet precipitate on dilution with water.—Dyes: cotton red from a soap bath, Appearance of dyestuff: yellowish brown powder.—In water: very sparingly soluble with brownish yellow colour.—On addition of hydrochloric acid to the aqueous solution: brown precipitate. —Dilute acetic acid : brown precipitate.—On addition of caustic soda: solution becomes reddish brown.—In conc. sulphuric acid : reddish violet solution ; brown precipitate on dilution with water. —Dyes: unmordanted cotton yellow from a soap bath. _ Gladioline II is a mixed tetrazo dyestuff from benzidine and naphthionic acid, As third component the Gladiolines are said 34487186 of the Albany Aniline Co, Ee ] [1] Constitutional Formula. NH,a (SO. Na), [1] NH, Cayo CoH. O,H, [4] -N=N- [2] CyoHt,{ [4] SO,Na [2] OH C,H, [4] -N=N- [1] C,H, [6] SO,Na i [8] $O,Na H, [4] -N=N-[1] C,H, [4] 0H [1] | C,H, [4] - N=N - [1] OH, [4] 00,H, 2] OH CoH, [4] [1]0H 2] CO,H [1] 0H [3] OH O,H, [4] -N=N- C,H{ FI C,H, [4] -N=N-[4] CyHs{ [1] 0H [2] CO,Na C,H, [4]-N=N-,,H, Ue Na C,H, [4]-N=N- C.H,{ -~N=N-[1]C,,H,4 [6] SO,Na [8] SO,Na | No.| Commercial Name. Scientific Name. Empirical Formula. 181} Alkali Red. [D.] Sodium salt of CoH, N,0,8,Na, (No longer in com- diphenyl-disazo- merce. ) naphthionic-a- naphthylamine-di- sulphonic acid. 182} Congo P. [A. Sodium salt of CogH 1 gN,0,8,Na. : [4.] diphenyl-disazo- 2 A A phenol-$-naphthol- y-disulphonie acid. 183 | Diamine Scarlet B. Sodium salt of Cop HopN,0,8,Na, [0] dipheny1-disazo- aeiet E et ‘ phenetol-8-naphthol- Direct Red B. y-disulphonic acid. [W. N.] 184} Cloth Orange. Sodium salt of C,,H,,N,0,Na [By.] diphenyl-disazo- ¥ resorcinol-salicylic acid. 185} Cloth Brown R. Sodium salt of CooN,.N,0,SNa, [By.] diphenyl-disazo- $ 7 salicylic-naphthol- sulphonic acid. 186} Cloth Brown G. Sodium salt of Croktrgt 40;Na [By] diphenyl-disazo- "> ‘ dioxy-naphthalene- salicylic acid. 187} Benzo Orange R. Sodium salt of CoH gN,O,SNa, [By] [4] diphenyl-disazo- nets o Tse ss salicylic-naphthionic- acid. 188| Alkali Yellow R. Sodium salt of CagHigNgO cease [D.] dipheny]-disazo- salicylic-dehydrothio- toluidine-sul phonic acid. C,H, [4] -N=N-—C,H Gina {i C,H,[4]- [1]OH H, [4] Nowe Css t31 00, O,H, [4] -N=N- [1] CyyE{ [1] 0H O,H, [4] -N=N- CpHy{ 12] 0O,Na C,H, [4] -N=N - [2] C,H, [1] OH 2]CO,Na _N-NHT4 ANU Na0, sta] oude< se [2] OH [7] OH [1] NH, [4] SO,Na Jey H,| | Method of Preparation. Year of Discovery. [eee Discoverer. Patents. Literature, Dani & Co. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: red powder.—In water: red solution.— In alcohol: slightly soluble-—On addition of hydrochloric acid to the aqueous solution: blue precipitate.—On addition of caustic soda: no change.—In conc. sulphuric acid: blue solu- tion; reddish blue precipitate on dilution with water.— Dyes: cotton red from a salt bath. Diazo ceed Combined with 1 mol. 1 mol. a- benzidine. | naphthylamine disulphonic acid (of Ger. Pat. 41957) + 1 mol. naphthionic acid, 1 mol. 1 mol. B- benzidine. naphthol-di- sulphonic acid G(y) + 1 mol. phenol. Ethylation of the dyestuff from benzidine, B-naphthol-disul- phonic acid G, and phenol (No. 182). 1 mol. 1 mol. salicylic benzidine. acid +1 mol. resorcinol, 1 mol. 1 mol. salicylic 4 benzidine. acid+1 mol. : ~ naphthol- 7 monosulphonic | acid, , . . q 1 mol. 1 mol. salicylic : benzidine. acid+1 mol. : dioxynaph- thalene (2:7). 1889. 1887, 1887, 1887. G. SCHULTZ. ACTIENGESELLSCH. F. ANIL. FABRIKN. Eng. Pat. 22136 (amended). Ger. Pat. 4095496, A. WEINBERG. L. CassELLA & Co. Eng. Pat. 12560®. Am. Pat. 426345. Appearance of dyestuff: red powder.—In water: red solution.— In alcohol: slightly soluble. —On addition of hydrochloric acid to the aqueous solution: dark brown precipitate.—On addition of caustic soda: solution becomes brown. —In conc. sulphuric acid: reddish violet solution ; dark brown on dilution with water.—Dyes: unmordanted cotton red from a salt bath. Appearance of dyestuff: reddish crystalline powder.—In water: red solution.—In alcohol: slightly soluble.—On addition of hydrochloric acid to the aqueous solution: brownish red.—On addition of caustic soda to the aqueous solution: no change. Ger. Pat. 45084°°, dependent In conc. sulphuric acid: violet solution; brown on dilution.— on 40954. E. FRANK & C. DuISBERG. G. SCHULTZ. Fr. Bayer & Co. Dyes: wool and silk scarlet from an acid or neutral bath, cotton from an alkaline bath. Appearance of dyestuff: reddish brown powder.—In water: yel- lowish brown solution.—In alcohol: yellowish brown solution.— On addition of hydrochloric acid to the aqueous solution: Eng. Pats. 2213°6 and 6687% brown precipitate.—On addition of caustic soda: solution be- (amended). Ger. Pat. 44797%, Employment : Ger. Pat. 5218389, comes red and (if concentrated) gives a red precipitate.—In conc. sulphuric acid: reddish violet solution; brown precipitate on dilution with water.—Dyes: chrome mordanted wool brownish orange. J. Soc. Dyers a Colorists, 1889, 170. E. Frank & C. DuIsBera. G. ScHULTZ. Fr. BAYER & Co. Appearance of dyestuff: dark brownish red powder.—In water: reddish brown solution.—In alcohol: insoluble.—On addition of hydrochloric acid to the aqueous solution : brown precipitate. Eng. Pats. 2213% and 6687° —In cone. sulphuric acid: bluish violet solution ; reddish brown (amended). precipitate on dilution with water.—Dyes: chrome mordanted Ger. Pat. 4479787, wool brownish red. Enuployment : Ger. Pat. 521839, J. Soc. Dyers and Colorists, 1889, 170. E. FRANK & C. DUISBERG. Fr. BAYER & Co. Appearance of dyestuff: dark brownish powder.—In water: brown solution.—In alcohol: slightly soluble.—On addition of hydro- Eng. Pat. 66878” (amended). chloric acid to the aqueous solution: brown precipitate.—On Ger. Pat. 447978. Employment : Ger. Pat. 52183°%. addition of caustic soda: solution becomes reddish brown.—In cone. sulphuric acid: reddish violet solution; brown precipitate on dilution.—Dyes : chrome mordanted wool brownish yellow. J. Soc. Dyers and Colorists, 1889, 170. 1 mol. 1 mol. salicylic benzidine. acid+1 mol. naphthionic acid. 1 mol. 1 mol. dehydro- benzidine. thio-p-tolui- dine-sulphonic acid +1 mol. salicylic acid. 1889. C. DuisperG & G. ScHULTz Fr. Bayer & Co. _| Appearance of dyestuff: brownish red crystalline powder.—In water: orange yellow solution.—In alcohol: nearly insoluble.— Eng. Pat. 2213° (amended). On addition of hydrochloric acid to the aqueous solution: Ger. Pat. 4479787, Danu & Co. Ger. Pat. 57095%, reddish violet.—On addition of caustic soda to the strong aqueous solution : reddish yellow precipitate.—In conc. sulphuric acid: violet blue solution; grayish violet precipitate on dilution with water.—Dyes : unmordanted cotton orange from an alkaline bath. Appearance of dyestuff: brownish yellow powder.—In water: opalescent yellow solution.—On addition of hydrochloric acid to the aqueous solution: brownish yellow precipitate.——On addi- tion of caustic soda to the aqueous solution: orange red pre- cipitate. —In conc. sulphuric acid: brownish red solution, — Dyes: unmordanted cotton yellow from a soap bath. one: a | ‘ - NH - C,,H,-S0,Na ] No.| Commercial Name. Scientific Name. Empirical Formula. 189; Brahma Red Sodium salt of C,,H,,N,0,S,Na, B & BB. [Z.] diphenyl]-disazo- 3 (No longer in com. | 2@phthionic-diphenyl- Monee ) amine-sulphonie acid. 190| Brahma Orange. Sodium salt of C,,H.,N,0,SNa, [Z] diphenyl-disazo- (No longer in com- salicylic-diphenyl- snare .) amine-sulphonie acid. 191} Brahma Red 6 B. Sodium salt of C,,H»,N,O,S,.Na, [Z.] diphenyl]-disazo- er naphthionic- (No longer in com- phenylnaphthylamine- merce.) sulphonic acid. 192| Naphthocyanine. Sodium salt of CaoHosN Oi joa hae [E. P.] diphenyl-disazo-bi- % (No longer in com- dioxynaphthalene- meres, } sulphonic acid. 193| Diamine Black R.| __ Sodium salt of Cy.HogN,0,9,Na, [C] diphenyl-disazo-bi- & : amidonaphthol- sulphonic acid. 194 | Diamine Fast Red. Sodium salt Cy9H,)N,0,SNa, [0.] of diphenyl-disazo- < ; : salicylic-amido- naphthol-sulphonic- acid. 195 | Diamine Brown V. Sodium salt of CygHagN,0,SNa [Ce] dipheny1-disazo- phenylene-diamine- amidonaphthol- sulphonic acid. 196| Diamine Violet N.| | Sodium salt of CoH oN sO.5,Na, [¢.] diphenyl-disazo-bi- amido-naphthol- sulphonic acid, Constitutional Formula, C,H, [4]-N=N - [4] C,H, [1] NH- 0,H, [1] NH, CH, [4] -N=N-[2] CoH SO,Na C,H, [4]-N= [1] 0H CH idle bes Mee CsHe{ fo} Go,ia C,H, [4] -N=N-(,H, [1] NH, C,H, [4] -N=N —[2] OH ie SO,Na [1] OH C,H, [4] -N=N-C,,H,J [5] 0H SO.Na (| [1] 0H C,H, [4] -N=N-C,,H,, [5] 0H S0,Na [2] NH, C,,H,4 [8] OH [6] SO,Na [2] NH, _-N=N-C,,H,4[8]0H [6] SO,Na CoH, [4] - N=nN- [1] | C.H, [4] [2] NH, =N - [1] C,,H,, [8] OH “lie 6] SO,Na [1] OH 2] CO,Na C,H, [4] - (11 | O,H, [4]-N=N- CH Ff [2] NH, C,H, [4]- N=N -C,,H,4 [8] OH (11 | [6] SO,Na 0,H,{4]-N=N- [4] CoHs{ Fa NE [2] NH, C,H, [4]-N=N-[1]C,,H,J [8] 0H | [2] NH, C,H, [4]-N=N-[1]C,,H,J [s] oH [6] SO,Na Ee -SO,Na — [4] C,H, [1] NH- C,H, -S0,Na es 8 ——S— ee a Serer BP Str Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Diazo Compound Pea aie, Discovery. Literature. Method of Employment. 1 mol. 1 mol. di- 1887. Ta. DIEHL. Appearance of dyestuff: reddish brown powder.—In water: red benzidine. phenylamine- G. C. ZIMMER. solution.—In alcohol: slightly soluble.—On addition of hydro- sulphonic acid Eng. Pat. 151 5487, chloric acid to the aqueous solution: blackish violet precipi- +1 mol, naph- Am. Pat. 380098. tate. —On addition of caustic soda: no change.—In cone. ianiniacid, sulphuric acid: blue solution: dark violet precipitate on dilution with water. —Dyes : unmordanted cotton red. 1 mol. 1 mol. di- LSS 72 Ta, DIEHL, Appearance of dyestuff: brown powder.—In water: brown solu- benzidine. phenylamine- G. C. ZIMMER. tion.—On addition of hydrochloric acid to the aqueous solution : sulphonic acid . Eng. Pat. 1515487, dark precipitate.—In conc. sulphuric acid : carmine red solution ; 1 mol. Am. Pat. 380098. black precipitate on dilution.—Dyes : unmordanted cotton orange. salicylic acid. 1 mol. 1 mol. phenyl- 1887. TH, DIEHL. Appearance of dyestuff: reddish brown powder.—In water: red benzidine. |naphthylamine- G. OC. Zimmer. solution.—In alcohol : slightly soluble.—On addition of hydro- sulphonic acid Eng. Pat. 1379888, chloric acid to the aqueous solution: violet black precipitate. = |) mol. Am. Pat. 401483. —On addition of caustic soda to the aqueous solution : colour naphthionic becomes brighter.—In conc. sulphuric acid: blue solution ; black acid. precipitate on dilution.—Dyes : unmordanted cotton red. 1 mol. 2 mols. 1888. Ewer & PIcK. Appearance of dyestuff: gray black powder.—In water: blue benzidine. monosulphonic Fr. Pat. 190065. solution.—In alcohol: insoluble.-—On addition of hydrochloric acid of (1:5) acid to aqueous solution : colour becomes violet.—On addition dioxy- of caustic soda to aqueous solution: colour becomes violet.— naphthalene. In conc. sulphuric acid: blue solution ; bluish violet precipitate on dilution.—Dyes : unmordanted cotton blue. 1 mol. 2 mols. amido- 1889. L. GANS. Appearance of dyestuff: black powder.—In water: violet black benzidine. naphthol-sul- L. CASSELLA & Co. solution.—In alcohol : sparingly soluble.—On addition of hydro- phonic acid G Eng. Pat. 16699%9, chloric acid to the aqueous solution: blue precipitate.—On (ory)in alkaline Ger. Pat. 5564889. addition of caustic soda to the aqueous solution ; violet solu- solution. tion.—In conc. sulphuric acid: blue solution; reddish blue pre- cipitate on dilution with water.—Dyes : unmordanted cotton black. 1 mol. 1 mol. amido- 1889, L. GANS. Appearance of dyestuff: brownish red powder.—In water: red benzidine. naphthol-sul- L. CAsseLta & Co. solution. —In alcohol: soluble.—On addition of hydrochloric phonic acid G Eng. Pat. 16699. acid to the aqueous solution: brown precipitate.—On addition (or y) in acid Ger. Pat. 55648°9, of caustic soda to the aqueous solution : no change.—In conc. solution +1 sulphuric acid: reddish blue solution; on dilution with water mol. salicylic brown precipitate. Dyes : unmordanted cotton red. acid. 1 mol. 1 mol. amido- 1889. L. GANS. Appearance of dyestuff: blackish powder.—In water: insoluble benzidine. naphthol-sul- L. Cassetta & Co. cold, sparingly hot to a brown red solution.—In alcohol: brown- phonic acid G Eng. Pat. 16699®. ish red solution. —On addition of hydrochloric acid to the (ory) +1 mol. aqueous solution : chocolate brown precipitate.—On addition of m-phenylene- caustic soda to the aqueous solution: purplish brown preci- diamine. pitate.—In cone. sulphuric acid: bluish violet solution ; purplish brown precipitate on dilution.—Dyes : unmordanted cotton dark violet brown. 1 mol. 2 mols. amido- 1889. L. GANS. Appearance of dyestuff: blackish brown powder.—In water : red- benzidine. naphthol-sul- L. CAssELLA & Co. dish violet solution.—In alcohol: insoluble.-—On addition of phonic acid G (or y) in acid solution. Eng. Pat. 166998, Ger. Pat. 55648%9. hydrochloric acid to the aqueous solution: violet black pre- cipitate.—On addition of caustic soda to the aqueous solution : no change.—In conc. sulphuric acid: greenish blue solution ; reddish violet precipitate on dilution.—Dyes: unmordanted cotton violet. [ 106 No. | Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula, 197 | Diamine Blue BB. ee ee - _ | Coplay N,01,8,Na, [1] NH, + ipheny]-disazo-bi- Le] amidonaphthol- C,H, [4] - N=N-C,,H, [8] 56a disulphonic acid. Ve So ne gNa 1] [1] NH, 8] OH CoH, [4] -N=N-C,)H, i SO,Na [6] SO,Na 198! Diamine Bronze Sodium salt of C.,.H,.N.0,,S,Na 1] 0H G. [C.] diamidobenzene-azo- SOs Melee ae CH, 4] N= Nee OoH,{ FI CO.Na cee disulphonaphthol-azo- : SRL prmetles C,H, [4] -N=N [1] OH acid. H,~ [3] SO.Na 3 3 [4] -N=N[8] [6] SO,Na H,4 [3] NH, [1] NH, 199| Diamine Green B. Sodium salt C.,H,.N.0,)S.Na, C,H, [4] -N=N — [4] C,H, [1] OH [C1] of dipheny]-disazo- 1 [1] 0H : phenol-disulpho- amidonaphthol-azo- C,H, [4] -N= moe H, 8] NH, nitrobenzene. CH (1]-N=N 2| [3] SO,Na 6" 4) 4] NO, [6] SO,Na 200| Carbazol Yellow. Sodium salt of ,H,,Ny0,Na, [1] OH B carbazol-disazo- C2 Hh oN i C, Hi N=N- C, H, + [B.] a PEDO ane As CO,Na bi-salicylic acid. "SNH 1] OH C,H, -N=N-—C,o [2] 00,Na 201| Sulphone Azurine. Sodium salt of CHeN-O, bana, C,H,(SO,Na) — N =N —[1] C,,H, [2] NHC,H Pp By. | disulpho diphenyl 44btogt\ pUggN Gy oe ) [1] Cy oH, [2] 65 sulphone-disazo- pi-phanle B- C,H,(SO,Na) - N=N — [1] C,,H, [2] NHC,H, naphthylamine. i Sodi It of : , a aie rate phoorlsty ieee CaF Dae, C,H, a ee N-O,H, [1] OH : ; bi-salicylic acid. [1] | 3\ [2] CO,Na 1] OH C,H,[4] N =N - C,H shee C0,Na 203 Direct Red. Sodium salt of C.,H,,N,0,S,Na, 3|CH [A.] [By] phenyltoly]-disazo- ar ae lee Cyt oy N =N - [2] OH, [1] NH, : bi-naphthionic acid. [1] | 10° \ [4] SO,Na [1] NH, C,H, [4] -N=N —[2]C,,H, ie 4] 80.Ne 204} Cotton Bordeaux. Sodium salt of Con ta NN Onenite. 1]N [B] diphenylene-ketoxim- i i ie C,H, [4] -N=N —[2] C,H, { Le : disazo-bi- 3\ [2] [4] 0,Na naphthionic acid. [1] |" aa N-OH BATA N=N-[2]C,,H, te 2048 PN eee a ee ee ee ee eevee Method of Preparation. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: slate gray powder.—In water: reddish blue solution.—In alcohol: insoluble.—-On addition of hydro- chloric acid to the aqueous solution : no change.—On addition of caustic soda: no change of colour.—In conc. sulphuric acid : blue solution; violet on dilution with water.—Dyes: unmor- danted cotton blue. Appearance of dyestuff: blackish powder.—In water: insoluble cold, chocolate brown solution hot.—In alcohol: insoluble.—On addition of hydrochloric acid to aqueous solution: purple brown precipitate.—On addition of caustic soda: solution be- comes yellower.—In conc. sulphuric acid : bluish violet solution ; black precipitate on dilution.—Dyes: unmordanted cotton yel- lowish brown. Appearance of dyestuff: dark powder.—In water: dull green solution. —In alcohol: bluish green solution. —On addition of hydrochloric acid to aqueous solution : bluish black precipitate. —On addition of caustic soda: solution becomes yellower.—In conc. sulphuric acid: violet solution ; black precipitate on dilu- tion.—After reduction with zinc dust: becomes brigkt blue on paper.—Dyes : unmordanted cotton green shades. Appearance of dyestuff: brownish yellow powder. —In ‘water: brownish yellow solution.—On addition of hydrochloric acid to the aqueous solution: brown precipitate. —On addition of caustic soda: orange yellow solution.—In conc. sulphuric acid : violet blue solution ; brown precipitate on dilution with water.— Dyes : unmordanted cotton from a boiling alkaline bath. Appearance of dyestuff: dark grayish blue powder.—In water : blue solution.—In alcohol: dark blue solution.—On addition of hydrochloric acid to the aqueous solution : blue precipitate.— On addition of caustic soda: slow separation of a blue precipi- tate.x—In conc. sulphuric acid: violet solution; blackish violet precipitate on dilution with water.—Dyes: wool blue from a , neutral bath containing sodium sulphate, unmordanted cotton blue from a neutral or soap bath. Appearance of dyestuff: dark grayish brown powder.—In water : yellow solution.—In alcohol: yellow solution.—On addition of hydrochloric acid to the aqueous solution: dark precipitate.— On addition of caustic soda: solution becomes brown.—In conc. sulphuric acid: carmine red solution; yellowish brown precipi- tate on dilution with water.—Dyes : unmordanted cotton yellow. Year of Discoverer. Patents. Diazo Compound Bea, Discovery. Literature. 1 mol. 2 mols. amido-| 1891, M. HorrMann. benzidine. naphthol-di- L. CAssELLA & Co. sulphonie acid Eng. Pat. 1742%, H (in alkaline solution). The product | m-phenylene- 1891. M. HorrMann & C. Kroun. obtained by diamine. L. CASSELLA & Co. combining di- Eng. Pat. 6972%. azotised benzi- dine with sali- eylic acid and amidonaphthol- disulphonic acid H. 1 mol. 1 mol. p-nitro- 1891. |M. Horrmann & C. DAIMLER. benzidine. benzene-azo- L. CAssELLA & Co. amidonaphthol- Eng. Pat. 15725%. disulphonic acid and 1 mol. phenol. 1 mol. diamido- 2 mols. 1888. R. Bown. carbazol. salicylic acid. Bap. Antu. & Sopa FABRIK. Eng. Pats. 14478°8 & 14479%, Am. Pat. 401634, Ger, Pat. 4643858, Fr. Pat. 193212%, J. Soe. Dyers & Colorists, 1889, 106. 1 mol. benzi- | 2 mols. phenyl- 1883. P. GRIEss. dine-sulphone- B-naphthyl- Eng. Pat. 1099%, disulphonic amine. 1885. C. DuIsBERG. od: Ber. 22, 2459. Fr. BAYER & Co. Ger. Pats. 27954° and 33088®, J. Soc. Chem. Ind. 1890, 51, 55. J. Soc. Dyers and Colorists, 1889, 170. 1 mol. 2 mols. 1888. SANDMEYER. diamido- salicylic acid. J. R. Guiey & Co. phenyltolyl. Eng. Pat. 13767, Am. Pats. 406669 & 406670. Fr. BAYER & Co. Ger. Pat. 5283988. 1 mol. 2 mols. 1888. SANDMEYER. diamido- naphthionic J. R. Gerey & Co. phenyltolyl. acid. Eng. Pat. 13767°. Am. Pat. 447189", ACTIENGESELLSCHAFT FUR ANILINFABRIKATION. Ger. Pat. 53986. 1 mol. 2 mols. 1889. P. Juuivs. diamido- naphthionic Bap. ANiL. & SoDA diphenylene- acid. FABRIK. ketoxim. Eng. Pat. 20668°. Ger. Pat. 525968. Fr. Pat. 202804. Appearance of dyestuff: red powder.—In water: red solution.— In alcohol: slightly soluble with yellowish red colour.—On addi- tion of hydrochloric acid to the aqueous solution: dark blue precipitate.—On addition of caustic soda: red precipitate.—In conc. sulphuric acid: blue solution; dark blue precipitate on dilution with water. Appearance of dyestuff: reddish brown powder.—In water : bluish- red solution.—On addition of hydrochloric acid to the aqueous solution: blue precipitate.—On addition of caustic soda to the aqueous solution: bluish red precipitate.—In conc. sulphuric acid: blue solution; blue precipitate on dilution with water.— Dyes: unmordanted cotton bordeaux red. [7 108 No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 205 Cotton Red. Sodium salt of C5,HogNgO,S,Na. 2] CH, “ i [B.] o-m-ditoly]-disazo-bi- ue 4 CoH ale ie ee N —[2] C,H Hie NH ; naphthionic acid. [1] |" [3] CH, 10 [4] SO,Na C,H, is ‘ [1] NH, [4] = N=N- [2] One SO,Na 206 Azo Blue. Sodium salt of CasHo Ns OgSoN ay [3] CH ; p, ditolyl-disazo-bi- ae Fons CH ee OH ee a-naphthol- " [1] Le N= Ne [4] SO,Na p-sulphonie aci [4] SO,Na va (IA N=N — [2] Chott tt Oe CHle{ tire [1] oH 207 Congo Corinth B. Sodium salt of C,,H,,N,0,S,Na, f[3] CH, ditolyl-disazo- 4 Pa a) CoH; ([1JNH, [By] [A.] naphthionic- ls N= Ns [2] C,H; ([4] SO,Na e naphthol iy 4]_-N=N - fp] G,H1,{ [4] 805% p-sulphonie acid. Se jot45 : C7 3 [3] CH, [1] OH 208; Benzopurpurine Sodium salt of Cy,HogN g0,9.Nay 3] CH, i Be ditolyl-disazo-bi- | .** ”° = Ce Hae N=N- (2) Gen ee Bult Ad naphthionic acid. | 10°"5 | [4] SO,Na 4]S0,Na [4] -N=N — [2] C,H, { 4180 CoHs\ [3] CH, Dg 209} Benzopurpurine Sodium salt of CO, HN,O S.Na, 3} CH rant ditolyl-disazo-bi- saa6" 6 6M a 82 CH Hy e as N= [2] Oo [1] NH, [A.] [B.] a-naphthylamine- [1] 10° | [5] SO,Na .| [B. sulphonic acid. [4] -N=N-[2] C,H te SO,Na a 10°"5 CH iS] OH, [1] NH, 210 | Benzopurpurine B. Sodium salt of C.,H,.N,O,S.Na. 3] CH, By) LA] ditolyl-disazo-bi- BF ao oie S aa CHs{ a 2 Ne N-{1]¢,,8 [2] NH, | B-naphthylamine- (1] | 10°" 5\ [6] SO,Na B-sulphonic acid. [4] -N=N (eee [6] SO,.Na sy biases 10-5) [91N Os is [3] CH, [2] NH, 211} Deltapurpurine Sodium salt of C,,HgN,O,S.Na, ([3] CH, ee B-naphthylamine- : gina [By.] [A.] sulphonic acid. i i [4] -N=N-[1]¢,,H ae SO,Na { ie oo ng A @,H, [3] CH, [2] NH; 212| Brilliant Congo R.| Sodium salt of C.,H,.N,0,8.Na. var flo) Gi 2 ditolyl-disazo- oF ee ae CoH, [2] NH, [4.] [By] Siuaphrigiaatne. (ele N= N— [1] CyoHs [6] SO,Na pee ne [1] [2] NH, B-naphthylamine- [4] - — [1] C,,H,3 [3] SO,Na 5 F 10 3 disulphonic acid. C,H, [3] CH, : 6]S0,Na * Benzopurpurine 4 B has also appeared in commerce under the following names + } This dyestuff is formed by dir eo combination of tetrazoditolyl with a mixture of equal parts of 6- and 6-sulphonie acids, and obtained by combining tetrazoditolyl with —— ee foo 4 Diazo Compound from 1 mol. o-m-tolidine. 1 mol. tolidine. 1 mol. tolidine. 1 mol. tolidine. 1 mol. tolidine. 1 mol. tolidine. 1 mol. tolidine. 1 mol. tolidine. Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Bee acsa lin Discovery. Literature. Method of Employment. 2 mols. 1889. G. KORNER. Appearance of dyestuff: red powder.—In water: red solution.— naphthionic Bap. Antz. & Sopa On addition of hydrochloric acid to the aqueous solution : acid. FABRIK. dark blue precipitate.—On addition of caustic soda to the Eng. Pat. 13558®, aqueous solution: no change.—In conc. sulphuric acid: blue Am. Pat. 429350, solution; dark blue precipitate on dilution with water.—Dyes : Ger. Pat. 5 459989, dependent unmordanted cotton scarlet red from an alkaline bath. upon 287538. 2 mols. 1885. C. DuIsBERG. Appearance of dyestuff: bluish black powder.—In water: violet a-naphthol- Fr. Bayer & Co. solution.—On addition of hydrochloric acid to the aqueous monosulphonic Eng. Pat. 95108 (amended). solution : violet precipitate.—Dilute acetic acid: no change.— acid NW. Am. Pat. 366078. On addition of caustic soda: the solution becomes magenta red. Ger. Pat. 3534185, —In conc. sulphuric acid: blue solution; violet precipitate on dilution with water.—Dyes: unmordanted cotton grayish violet from a soap bath. 1 mol. 1885. S. Prarr. Appearance of dyestuff : grayish black powder.—In water : magenta naphthionic ACTIENGESELLSCHAFT FUR red solution.—On addition of hydrochloric acid to the aqueous acid +1 mol. ANILINFABRIKATION. solution : violet precipitate.—Dilute acetic acid : solution rather a-naphthol- Eng. Pats. 1 52968 ; 221386 ; bluer.—On addition of caustic soda to the aqueous solution : monosulphonie 668786, colour becomes cherry red.—In conc. sulphuric acid: blue solu- acid NW. Am. Pat. 358865. tion; violet precipitate on dilution.—Dyes : unmordanted cotton Ger. Pat. 39096, 2nd addn. brownish violet from a soap bath. to 28753. 2 mols. 1884. G. Scuu.tz. Appearance of dyestuff: brown powder.—In water: brownish red naphthionic C. DuISBERG. solution.—On addition of hydrochloric acid to the aqueous acid. ACTIENGESELLSCHAFT FUR solution : blue precipitate.—Dilute acetic acid: brown precipi- ANILINFABRIKATION. tate.—On addition of caustic soda: no change of colour.—In Ger. Pat. 35615®, 1st addn. conc. sulphuric acid : blue solution; blue precipitate on dilution to 28753. with water.— Dyes: unmordanted cotton red from an alkaline Fr. BAYER & Co. bath, wool from a neutral bath. Eng. Pat. 38039. Am. Pat. 329632. 2 mols. 1885. S. PFAFF. C. Duisperc. | Appearance of dyestuff: red powder.—In water : orange red solu- a-naphthyl- ACTIENGESELLSCHAFT FUR tion.—On addition of hydrochloric acid to the aqueous solu- amine-mono- ANILINFABRIKATION. tion: blue precipitate.—Dilute acetic acid: blue precipitate.— sulphonic acid s Ger. Pat. 35615%°, 1st addn. On addition of caustic soda to the aqueous solution: red ‘ to 28753. solution.—In conc. sulphuric acid: blue solution ; blue precipi- Fr. Bayer & Co. tate on dilution with water.—Dyes : unmordanted cotton red from Eng. Pat. 380385 (amended). el NL 2 mols. 1885. C. DUISBERG. Appearance of dyestuff: brown powder.—In water: reddish brown B-naphthyl- ACTIENGESELLSCHAFT FUR solution.—On addition of hydrochloric acid to the aqueous amine-mono- ANILINFABRIKATION. solution: brown precipitate. —Dilute acetic acid: solution be- sulphonic acid Ger. Pat. 35615*, 1st addn. comes brown.—On addition of caustic soda to the aqueous Br. to 28753. solution: no change.—In conc. sulphuric acid: blue solution ; Fr. Bayer & Co. dark brown floceulent precipitate on dilution with water.—Dyes : Eng. Pat. 3803®° (amended). unmordanted cotton red from an alkaline bath. Am, Pat. 329638. 1 mol. 1886. Fr. BAYER and C. Duisperc.| Appearance of dyestuff: reddish brown powder.—In water: bright P-naphthyl- Ber. 20, 1430. yellowish red solution. —On addition of hydrochloric acid to amine-6-sul- Fr. Bayer & Co. the aqueous solution : brown precipitate.—Dilute acetic acid : phonic acid + Eng. Pat. 5846°. solution becomes brown.—On addition of glacial acetic acid: 1 mol. Ger. Pat. 420215°, dependent brown precipitate.—On addition of caustic soda to the aqueous B-naphthyl- upon 28735. solution: red precipitate. Magnesium sulphate: precipitates amine-sulphonic the ‘“‘diamine red” which is present.—In conc. sulphuric acid : acid Br.+ blue solution; brown precipitate on dilution. —Dyes: unmor- _ danted cotton red from an alkaline bath. 1 mol. 1886. S. Prarr and R. Kriicgenrr.| Appearance of dyestuff: brown powder.—In water: brownish red B-naphthyl- ACTIENGESELLSCHAFT FUR solution.—On addition of hydrochloric acid to the aqueous amine mono- sulphonic acid Br. + 1 mol. B-naphthyl- amine disul- phonie acid R. the B- and 6-acids in succession. ANILINFABRIKATION. Eng. Pat. 6687°7 (amended). Ger. Pat. 4109587, 8rd addn. to 28753. Eclipse Red, Fast Scarlet, Azamine 4 B, Victoria Red, Imperial Red, etc. ‘consequently contains also Benzopurpurine B and Diamine Red 3 B; ep. Ber. 20, 3160. solution : reddish brown precipitate.—Dilute acetic acid : colour somewhat bluer.—On addition of caustic soda to the aqueous solution: reddish yellow precipitate soluble in much water.— In cone. sulphuric acid: blue solution ; brownish black precipi- tate on dilution—Dyes : unmordanted cotton red from a soap bath. Diamine Red B [4.] [By.] is the pure dyestulf pad 2 Bale | No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 213} Congo Red 4 BR. | Sodium salt of ditolyl-/ ©,,H,,N,0,SNa C,H ee CH [1] NH disazo-resorcinol- 4 Ne N —[2]C,,H s{ & [4.] [By] ohare mea PU P10 ‘VAIS 4)-N=N-[4] 0H Ai C Pinta cH, [4] [3] OH enn vearine ee Sodium salt of C,gH,,N,0,Na, OH {fle CH, [1] OH es ge ditolyl-disazo-bi- 4 N= N -—C,H 2{ Leuehlaa) salicylic acid. [1] ; La] : re ey pee 4]|-N=N-(O,H 1 C Re He ae [1] OH 215 Orange | Sodium salt of C,,H.,N,0,9Na. ee) ene [6] CH : SE ee e ditolyl-disazo-o-eresol-| “ ** °° CoHs\ 14] N=N-[4] C.H, Ie OH sig carboxylic-m-tolylene- [2] CO,Na diamine-sulphonic 2 acid. [1] [5] SO,Na ([4]-N = N— [4] oyu es CoH F3] CH, [3] N 2 [6] CH; 216 O e Sodium salt of C,.H..N.S,0,Na, 6] CH amr ) | aitolyl-disazo-bi- | “2° 2882-6" oe ie CH, HINES eS m-tolylene-diamine- 6 [4]- N= N- [4] Cs “H [3] NEL sulphonic acid. [5] 80 a Me 3 [1] [5]SO,Na ([4]-N=N-[4) on) Ee C ols) (3) CH, [1] 2 [6] CH, 217 Rosazurine G. Sodium salt of C.,H)N,0,5,Na, C,H ([3] CH, [2] NHC,H rae ditolyl-disazo-ethyl- 3\[4]- Ne N—([1}C),5; ae B-naphthylamine- af ltl— RN oe ealiinnte acid. CoH, [3] CH, Bape 218! Rosazurine B. Sodium salt of C,,H.,N,0,5.Na, OH, afr [3] CH, [2] NHC,H ditolyl-disazo-bi-ethy]- Ae N -[1]0,,H; 2°*5 [By] ss a ile 1015 £7] SO,N B-naphthylamine- °\[7] SO,Na salphetiis acid. [1] [4]-N=N-[1]0,H ee SO,Na CsHa{ 34 CH. 105) [2] NHO,H, 219| Diamine Red 3 B.| Sodium salt of C,,H,.N,O,S.Na. 3] CH 4 [2] ditolyl-disazo-bi- | M3 P82 CoHs{[s] -N=N [1] OH, tr] $0, Na Deltapurpurine Hon geben [1] | [7] SO, Na 7 B. CE. Hea —-N= he Chet 134 NH, [By.] [4.] °° \[8] CH, f eo. | Method of Preparation. Behaviour with Reagents. Shade and Dyeing Properties, Method of Employment. Appearance of dyestuff: brown powder.—In water: brownish red solution.—On addition of hydrochloric acid to the aqueous solution : violet precipitate.—Dilute acetic acid : brown precipi- tate.—On addition of caustic soda to the aqueous solution: scarcely altered.—In conc. sulphuric acid: blue solution ; violet precipitate on dilution with water.—Dyes: unmordanted cotton red from a soap bath. Appearance of dyestuff: yellowish brown powder.—In water: brownish yellow solution.—On addition of hydrochloric acid to the aqueous solution: brown flocculent precipitate.— Dilute acetic acid: brown floceculent precipitate.—On addition of caustic soda to the aqueous solution : reddish brown colour.— In cone. sulphuric acid: reddish violet solution ; brown floccu- lent precipitate on dilution with water. Appearance of dyestuff: yellowish red powder with bluish cast.— In water: brownish yellow solution.— Dilute acetic acid: no change.—On addition of hydrochloric acid to the aqueous solution : yellowish brown flocculent precipitate.—On addition of caustic soda: solution becomes reddish orange.—In conc. sulphuric acid: magenta red solution; brown precipitate on dilution with water.—Dyes: unmordanted cotton orange, Appearance of dyestuff: brownish red powder.—In water : orange solution.—Dilute acetic acid: reddish opalescent solution.—On addition of hydrochloric acid to the aqueous solution: bluish red floceulent precipitate.—On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: brown solution ; reddish precipitate on dilution with water.—Dyes: un- mordanted cotton reddish orange. Appearance of dyestuff: reddish brown powder.—In water : cherry red solution.—On addition of hydrochloric acid to the aqueous solution: reddish violet precipitate.— Dilute acetic acid: no change.—On addition of caustic soda to the aqueous solution: searcely altered.—In conc. sulphuric acid: blue; reddish violet precipitate on dilution with water.—Dyes: unmordanted cotton bluish red from an alkaline bath. Appearance of dyestuff: brown powder.—In water: cherry red solution.—On addition of hydrochloric acid to the aqueous solution : reddish violet precipitate.—Dilute acetic acid: colour somewhat darker.—On addition of caustic soda to the aqueous solution: no change.—In conc..sulphuric acid: blue solution ; violet precipitate on dilution with water.—Dyes: cotton bluish red from an alkaline bath. Year of Discoverer. Patents. iiss Compound Peake ek Discovery. Literature. 1 mol. 1 mol. 1885. S. PRAFF. tolidine. naphthionic ACTIENGESELLSCHAFT FUR acid + 1 mol. ANILINFABRIKATION, resorcinol. Eng. Pats. 15296 and 2213%° (amended). Ger. Pat. 39096®, 2nd addn. to 28753. 1 mol. 2 mols. 1884, KE. Frank. tolidine. salicylic acid. Fr. BAYER & Co. Eng. Pat. 9606*4, Am. Pat. 329639. Ger. Pat. 31658%. 1 mol. 1 mol. 1888. Cur. Rupoupx and tolidine. o-cresotic acid B. PRIEBS. +1 mol. K. OFHLER. m-tolylene Eng. Pats. 4492%7 and 79978. diamine sul- Ger. Pat. 4723558, dependent phonic acid. on 31658 and 44797. 1 mol. 2 mols, 1886. P. FRIEDLANDER. tolidine. m-tolylene- B. Press. diamine-sul- K. OEHLER. phonic acid. Eng. Pat, 4492°7, Ger. Pat. 40905*, : 1 mol. 1 mol. ethyl-6-| 1886. E,. HASSENKAMP and : tolidine. naphthylamine- C. DUISBERG. 4 5-sulphonic acid Fr. Bayer & Co. i +1 mol. p- Eng. Pat. 17083°°, : naphthylamine- Ger. Pat, 41761%. 6-sulphonic acid. 1 mol. 2mols.ethyl-B-| 1886. EK. HASSENKAMP, tolidine. naphthylamine- Tr. BAYER & Co. 5-sulphonic Ing. Pat. 17083*°, acid. Ger. Pat. 41761®. 1 mol. 2 mols. 1886. |FR. BavErand C. DuIsBERG. aaa -naphthyl- Ber. 20, 2910, 3160. po uding. c Re. Fr. Bayer & Co. sulphonic acid. Eng. Pat. 4846%, Ger. Pat. 42021%, dependent upon 28753. L. CAssELLA & Co. Eng. Pat. 12908%, Ger. Pat. 48074. Appearance of dyestuff: reddish brown powder.—In water : spar- ingly soluble cold, easily on boiling.—On addition of hydrochloric acid to the aqueous solution: brown precipitate.—With acetic acid: brownish violet precipitate.—Magnesium sulphate: pre- cipitates the magnesium salt ; sparingly soluble in water ; insoluble in water containing hydrochloric acid.—On addition of caustic soda to the aqueous solution: red precipitate.—In conc. sul- phuric acid: blue solution; yellowish brown precipitate on dilution with water.— Dyes: unmordanted cotton red from an alkaline bath. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 220 Brilliant Sodium salt of ditolyl-| C,,H,,N,O,9,Na, CH f[8]CH [2] NH, Purpurine, [4.] | 98820 naphtnton: os) F4)_ N=N —[1] CoH,4 [3] $0,Na adel’ B-naphthylamine- [6]SO,Na disulphonie acid. [1] lyn ‘i yp fI4J-N=N- [2] CpoHs } C,H. [3] CH, [4]SO,Na 221| Congo Orange R. | Sodium salt of ditolyl-) C,,H,,N,O,S,Na, C,H, [3] CH, [2] NH, [A] inaece ieee 3\ [4] -N=N [1] O,H,4 [3] SO, Na aiealphonic acid. [1] | [6 SO, Na CH. f{4]-N=N-[1] C,H, [4] OC.H, OP \ 3) Gee 292|Diamine Blue 3B.| Sodium salt of | C,,H,,N,O,,8,Na 1] NH [a] ditoly]-disazo-bi- OIA ig C,H, [3] CH, a OH. ; amido-naphthol- 3\ [4] - N= N= C,H; N | disulphonie acid. a nate a ; [1] [6] SO, 6]SO,Na 2 3] SO,Na on,{ tio SS fy OH 6~'3\ [3] CH, . [1] NH, . 223 | Diamine Blue BX. | Sodium salt of ditolyl-| C,,H,,N-O,,S.Na., [3] CH, | [c] disazo-a-naphthol- savas oui 8 C ott ee Ne N - [2] C,,H th OH ; monosulphonic- 10°"5\ [4] SO,Na amido-naphthol- fl] [6] SO,Na : disulphonie acid. [3] SO,Na 4] — — [2] C,H C,H ft 1043) fg] OH oe HT NH, ae ; 224 Azo Mauve. Sodium salt of C,,H,.N,0,S,Na, C,H, [3] CH, [0] ditolyl-disazo- 3\[4] -N =N -C,,H,(NH,) (OH) (SO,Na) a-naphthylamine- [1] ‘i N_N on? N H, 2 amido-naphthol- { [4] = TOs Oe disulphonie acid. e838) CHe 225| Diamine Red NO. | Sodium salt of ethoxy-| G, H,.N.O-S,Na. 3] 0C,H, [0] diphenyl-disazo- | 3 27NoOvS2Na2 C Hf -N=N—[1] CoH F61803 B-naphthylamine- 1] | ‘> 105 | (GL SO Na Sree, C,H, [4]-N=N-[1]¢,H Ww ae “hap 4 - 5 — = — 6-sulphonie acid. ake 10° *\ [2] NH, 226 |Diamine Yellow N.| Sodium salt of GC. Hew OLN. 3] CH, [C1] ethoxy-dipheny]- Toe al a C,H, aa N aN oe [1] 0H disazo-phenetol- [1] | ae A BALE >i salicylic acid. C,H, [4] -N=N-[4] C,H, [1] 00,H, 227| Diamine Blue B. Sodium salt of C.,Hy,N ,0,.8,Na, CH, [3] OCH, [2] OH [C1] OR AEE o's \f4]— Ne ore [1] C,,H,4 [3] $O,Na isazo-B-naphthol- 3 5-disulphonic- [1] [7] SO,Na a-naphthol- [4] SO,Na monosulphonie acid. C,H, [4]-N=N-[2] OyeHe tf an pod Se aay Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Diazo Compound eked Wich Discovery. Literature. Method of Employment. 1 mol. 1 mol. 1887. ACTIENGESELLSCHAFT FUR | Appearance of dyestuff: red powder.—_In water: red solution.— tolidine. B-naphthyl- ANILINFABRIKATION, In alcohol : yellowish red solution.—On addition of hydrochloric amine-disul- Eng. Pat. 668787, acid to the aqueous solution: black precipitate.—On addition phonic acid R Ger. Pat. 4109587. of caustic soda to the aqueous solution: red precipitate. —In +1 mol. Fr. Pat. 16072287, conc. sulphuric acid: blue solution; blue black precipitate on naphthionic 97581 dilution with water.—Dyes: unmordanted cotton red from an acid. Austr. Pat. oo7q°”. alkaline bath. Ital. Pat, Vol 21, 23033, Vol. 45, 348 Ethylation of the product 1889. BoRGMANN., Appearance of dyestuff: yellowish red powder.—In water : yellow- obtained by combining 1 mol. ACTIENGESELLSCHAFT FUR ish red solution.—In alcohol: slightly soluble.—On addition of tetrazoditolyl with 1 mol. of ANILINFABRIKATION. of hydrochloric acid to the aqueous solution: dark brown 8-naphthylamine-disulphonic Eng. Pat. 17957®, precipitate.—On addition of caustic soda to the aqueous solu- acid R and 1 mol. of phenol. Ger. Pat. 52328. tion : no change.—In conc. sulphuric acid: dark blue solution ; dark brown precipitate on dilution with water.—Dyes: unmor- danted cotton orange. 1 mol. 2 mols. amido- 1891. M. HorrmMann. Appearance of dyestuff: slate gray powder.—In water: violet tolidine, naphthol-di- L. CAssELLA & Co. solution.—In alcohol: insoluble.—On addition of hydrochloric sulphonic acid Eng. Pat. 17429. acid to the aqueous solution: bluer; violet precipitate with an H (in alkaline excess. —On addition of caustic soda: no change.—In conc. solution). sulphuric acid : blue solution; violet precipitate on dilution with water.—Dyes : unmordanted cotton blue. 1 mol. 1 mol. 1891. M. HorrMann. Appearance of dyestuff: dark powder.—In water: bluish violet tolidine. a-naphthol- L. CasseLLA & Co, solution.—In alcohol: slightly soluble-—On addition of hydro- monosulphonic Eng. Pat, 17429, chloric acid to the aqueous solution: violet precipitate. On acid NW. + addition of caustic soda: the solution becomes bluish red. —In 1 mol. amido- sulphuric acid : blue solution ; violet precipitate on dilution with naphthol-di- water.—Dyes : unmordanted cotton a deep blue. sulphonic acid igh 1 mol. 1 mol. amido- 1890. Cur. RuDOLPH. Appearance of dyestuff: blackish powder.—In water : violet solu- tolidine. naphthol-di- K. OEHLER. tion.—On addition of hydrochloric acid to the aqueous solution : sulphonic acid Ger. Pat. 1434%, violet precipitate.—Dilute acetic acid: colour rather bluer.—On +1 mol. a- addition of caustic soda to the aqueous solution: no change. naphthylamine. —In conc. sulphuric acid: blue solution; violet on dilution with water.—Dyes: unmordanted cotton blackish blue violet from an . alkaline bath. ~|1 mol. ethoxy- 1 mol. 1887. A. WEINBERG. Appearance of dyestuff: greenish crystalline powder.—In water : benzidine. B-naphthyl- L. Cassetua & Co. red solution.—In alcohol: sparingly soluble.—On addition of amine--sul- Eng. Pat. 1446487, hydrochloric acid to the aqueous solution : violet precipitate. phonic acid + Am. Pat. 380067. —On addition of caustic soda: no change.—In cone. sulphuric 1 mol. Ger. Pat. 4613487, acid: blue solution ; black precipitate on dilution with water.— B-naphthyl- Fr. Pats. 186566 and 186567. Dyes: unmordanted cotton red from an alkaline bath. amine-6-sul- J. Soc. Dyers and Colorists, 1889, phonic acid. 170. Ethylation of the product 1887. A. WEINBERG. Appearance of dyestuff: brownish yellow powder.—In water: obtained by combination of L. CAssELLA & Co. sparingly soluble.—In alcohol: more easily soluble.—On addi- 1 mol. of diazotised ethoxy- Eng. Pat. 1446487, tion of hydrochloric acid to the aqueous solution: greenish benzidine with 1 mol. of phenol Am. Pat. 380067. precipitate. —On addition of caustic soda to the aqueous and 1 mol, of salicylic acid. Ger. Pat. 4613487, solution : reddish yellow precipitate.—In conc. sulphuric acid : Fr. Pats. 186566 and 186567. violet solution ; greenish brown precipitate on dilution with water. J. Soc. Dyers and Colorists, 1889, —Dyes : unmordanted cotton yellow. 170. 1 mol. ethoxy- 1 mol. 1887. A. WEINBERG. Appearance of dyestuff: dark bronzy powder.—In water: blue benzidine. B-naphthol-6- L. CAssELLA & Co. solution.—In alcohol: insoluble.—On addition of hydrochloric disulphonic acid Eng. Pat. 14464°7, acid to the aqueous solution: blue precipitate.—On addition +1 mol. Am. Pat. 380067. of caustic soda: solution becomes reddish blue.—In conc. sul- 7 a-naphthol- Ger, Pat. 4613487. phuric acid: blue solution; blue precipitate on dilution with f monosulphonic Fr. Pats. 186566 and 186567. water.—Dyes : unmordanted cotton blue. acid NW. Ss ee oeeA PEs Scientific Name. No.| Commercial Name. Empirical Formula. Constitutional Formula. 228|Diamine Blue 3R.| Sodium salt of C,,H,,N,0.8,Na, [0] ethoxy-diphenyl- ‘ disazo-bi-a-naphthol- p-sulphonic acid. 229| Diamine Black B. Sodium salt of C,H sN,0,S,Na, [C.] ethoxy-diphenyl- ts disazo-bi-amido- naphthol-sulphonic acid. 230 Diamine Blue Sodium salt of CG. EogN Ojo, Nae Black E. ethoxy-diphenyl- z 0 disazo-amido- [C-] naphthol-mono- sulphonic-8-naphthol- 5-disulphonic acid. 231 Direct Red. Sodium salt of C,,HogN,0,S.Nay ea ethoxy-tolyl-phenyl- eA" ; (No longer in com- Sea -bi- d merce.) naphthionic acid. 232| Benzoazurine G. Sodium salt of CG, HosN OrpsoNeg [By.] dimethoxy-diphenyl- _ disazo-bi-a-naphthol- p-sulphonic acid. 233 Azo Violet. _ Sodium salt of O,,H,.N,0,8,Na, [By.] dimethoxy-diphenyl- i ee : disazo-naphthionic- a-naphthol-p- sulphonic acid. 234 Heliotrope. Sodium salt of Cotas Ny Oasen al [By.] [4.] [LJ diethoxy-diphenyl- ita Th ae De disazo-bi-ethyl-8- naphthylamine-f- sulphonic acid. 235 | Benzoazurine 3 G. Sodium salt of Os,Ho,N,0 So Na, [By.] diethoxy-diphenyl- p-sulphonic acid. disazo-bi-a-naphthol- spi 2] OCHS ayy Atal -Ns tat (f1] $0,Na CoH, [4] - N=N —[2] CioHs i] cr Gant tel Dots [2] NH, *\[4] -N=N - [5] CoH, if OH [1] ; [6]S0,Na [6] SO,Na O,H, [4] -N=N-[5] cyt OH . [2] 2 ou, ([3] OCH; [2] OH 6 Ale -N=N-[]] ct SO,Na 1] [7]SO,Na [2] NH, C,H, [4] -N=N-[5] C,H, 13 OH [6]SO,Na camo Gn: [5] OO, H, INH ny] Mi-N=w 121 oH (ET2D O,H, [4]-N=N -[2] OH, {Fy a o,ni,{{3] OCH "| 3\[4]- -[2] Cet {td 50.Na : [4]S0,Na Ou. Ms a me slit be [3] 0CH, ie [4] -N=N -[2]C,,H, te ae f [4]SO,Na C,H, a OCH, i cuts] me [3] OCH aa [4]-N é N -[1] C,H, te s0.N [7] SO, Na 7 H, lex Ree =N-[1]C,,H, {t3) NHC gH [3] OCH ah [4]-N is N —[2]C,)H, {ts sONe ug) [5] SO, Na OH {i ee N -(2] CoH s{ ty OH a ; 4 . — | Method of Preparation. neg . Diazo a Se Combined with UNS y: 4 |1 mol. ethoxy- 2 mols. 1887. benzidine. a-naphthol- monosulphonic acid NW. 1 mol. ethoxy- 2 mols. 1889. benzidine. |amidonaphthol- sulphonic acid G (or y) in alkaline solution. 1 mol. ethoxy- 1 mol. 1889. benzidine. B-naphthol-6- disulphonic acid +1 mol. amidonaphthol- monosulphonic acid G (or y) in alkaline solution. 1 mol. 2 mols. 1887, diamidoethoxy-| naphthionic tolylphenyl. acid. 1 mol. 2 mols. 1885. dianisidine. a-naphthol- sulphonic acid NW. 1 mol. 1 mol. 1886. dianisidine. naphthionic acid + 1 mol. a-naphthol- monosulphonic acid NW. ‘1 mol. 2 mols 1887 dianisidine. ethyl-p- naphthyl- amine-6- sulphonic acid. 1 mol. 2 mols. 1885. dianisidine. a-naphthol- monosulphonic acid L. Discoverer. Patents. Literature. A. WEINBERG. L. CAssELLA & Co. Eng. Pat. 14464°”, Am. Pat. 380067. Ger. Pat. 4613487, Fr. Pats. 186566 and 186567. L. GANS. L. CASSELLA & Co. Eng. Pat. 16699°%. Ger. Pat. 5564889, T. BALDENSPERGER. J. Soc. Chem. Ind. 1891, 762. A. KErrisz. Chem. Zeit. 15, 701. L. GANS. L. CASsELLA & Co. Eng. Pat. 16699*°. Ger. Pat. appl. C. 3120. H. MULLER. J. R. Geiay & Co. Ger. Pat. 42006. PorrRRIER and ROSENSTIEHL. Eng. Pat. 12355°”. C. DUISBERG. Fr. BAveR & Co. Eng. Pat. 14424°° (amended). Am. Pat. 357273. Ger. Pat. 38802°. C. DuISBERG. Fr. Baver & Co. Eng. Pats. 14424% & 7283%°, Ger. Pat. 40247%, addn. to 38802. E. HassENKAMP and C. DUISBERG. Fr. BAver & Co. Eng. Pat. 17083%, Ger. Pat. 4820487, addn. to 4176155, C. DuisBEre. Fr. Bayer & Co. Eng. Pat, 144248, Am. Pato) 2tes Ger. Pat. 38802. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: black powder with greenish lustre.—In water : easily soluble hot, with reddish blue colour.—In alcohol : sparingly soluble.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda: solution becomes reddish violet.—In conc. sulphuric acid: dark blue solution ; violet precipitate on dilution with water.—Dyes : unmordanted cotton reddish blue, Appearance of dyestuff: black powder. —In water: blackish blue solution.—In alcohol: sparingly soluble.—On addition of hydro- chloric acid to the aqueous solution: blue precipitate. —On addition of caustic soda to the aqueous solution: uo change. —In cone. sulphuric acid: blackish blue solution; reddish blue precipitate on dilution with water.—Dyes: unmordanted cotton blue black.—By diazotisation on the fibre and combination with naphthols, etc., extremely fast deep “ingrain ” blacks are obtained. Appearance of dyestuff: black powder.—In water: blackish blue solution.—In alcohol: insoluble.—On addition of hydrochloric acid to the aqueous solution: blue precipitate. —On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: blackish blue solution ; blue precipitate on dilu- tion with water.—Dyes : unmordanted cotton a black blue. Appearance of dyestuff: dark brownish red powder.—In water : red solution.—In alcohol: slightly soluble. —On addition of hydrochloric acid to the aqueous solution: dark precipitate. —On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: violet solution ; violet preci- pitate on dilution with water, redissolving on further dilution.— Dyes : unmordanted cotton red. Appearance of dyestuff: bluish black powder.—In water: blue violet solution. —On addition of hydrochloric acid to the aqueous solution: violet precipitate.— Dilute acetic acid: no change.—On addition of caustic soda to the aqueous solution : magenta red coloration.—In conc. sulphuric acid: blue solution, bluish violet precipitate on dilution with water.—Dyes: cotton blue from an alkaline bath; the dyed material becomes red on heating, blue again on cooling. Appearance of dyestuff: blackish blue powder.—In water : reddish violet solution.—On addition of hydrochloric acid to the aqueous solution: blue precipitate.— Dilute acetic acid: blue violet colour.—On addition of caustic soda to the aqueous solution : magenta red colour.—In conc. sulphuric acid ; blue solution, blue precipitate on dilution with water.—Dyes: unmordanted cotton bluish violet from a soap bath. Appearance of dyestuff: brown powder.—In water: magenta red solution.—On addition of hydrochloric acid to the aqueous solution : violet precipitate.—Dilute acetic acid : colour becomes reddish violet.—On addition of caustic soda to the aqueous solution: scarcely any change.—In conc. sulphuric acid: blue solution, bluish violet precipitate on dilution with water.—Dyes : unmordanted cotton reddish violet from an alkaline bath. Appearance of dyestuff: gray black powder.—In water: bluish violet solution.—In alcohol: violet solution.—On addition of hydrochloric acid to the aqueous solution: bluish violet pre- cipitate.—On addition of caustic soda to the aqueous solution : colour becomes violet red.—In cone. sulphuric acid: blue solu- tion, violet precipitate on dilution with water.—Dyes: unmor- danted cotton blue from an alkaline bath. [ ae No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 236| Benzopurpurine 10 B. [By.] [¢.] 5 G. [By.] 239; Congo Brown R. [A.] 240| Congo Brown G. [4.] 241| Benzo Brown G. [ By.] 242| Benzo Brown B. [By. ] 237 | Diamine Sky Blue. 238| Brilliant Azurine Sodium salt of dimethoxy-diphenyl- disazo-bi-naphthionic acid. Sodium salt of diethoxy-diphenyl- dlisazo-bi-amido- naphthol-disulphonic acid. Sodium salt of dimethoxy-diphenyl- disazo-bi-dioxy- naphthalene- sulphonic acid. Sodium salt of sulpho-naphthalene- azo-resorcin-azo- diphenyl-azo-salicylic- acid. Sodium salt of sulpho-benzene-azo- resorcinol-azo- diphenyl-azo- salicylic-acid. Sodium salt of sulpho-benzene-azo- phenylene-brown. Sodium salt of sulpho-naphthalenc- azo-phenylene-brown. C,,H,.N,O,8,Na, CgHogN gO i_8,Na, C,,H,,N,0,,8,Na, C,;Ho.N,O,8Na, Cy, HopN (OgSNa, C39 Ho,Nj.0,S,Nay 1 CyagHogN 12065,Na, Cy oH [1] NH, [2] CoH, ee SO,Na — [2] Chetta pid ae 17 {[3]0CH CiHalfa] van = Pains = CyHy{ Fa OCH, [3] OCH, [1] NH, [6]SO,Na - [6]S0,Na [4]-N=N-C,H [3]SO,Na CHelfs}00,8, NINH, [3] 0CH ane Raat -N=N- CoH, i] OH [4]S0,Na * [4]80,Na 4]-N=N-C,,H,,[8] 0H C.Hle{ fs} ocH, Hee C,H, [4]-N=N-[4] C,H { ty CO,Na C,H 41—-N=N—-[4 110H cytes (eho LO=56: [4] SO,Na 0,H,[4]- N=N -[4]C,H s(ta]00..0 C,H, [4]- 4 1]OH presence oH, H1S0,Na ae ae S0,Na MAN) -N=N-BD cu (DINE ogn,{- N=N -[4] She CEH C Hatta mie ah (ts SO,Na 6 bJ-N=N-Bl\o, i" »{RINBs OH (ya [3] NH, 4 Is] -N=N- loom, [1] NH, [1] -N=N-[2] [3] NH, [4]SO,Na 77 peels | Method of Preparation. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff : brownish red powder.—In water : carmine red solution.—In alcohol : red solution.—On addition of hydro- chloric acid to the aqueous solution: blue precipitate. —On addition of caustic soda to the aqueous solution : red flocculent precipitate. —In conc. sulphuric acid: blue solution, blue pre- cipitate on dilution with water.—Dyes: unmordanted cotton carmine red from an alkaline bath. Appearance of dyestuff: bluish gray powder.—In water: pure blue solution.—In alcohol: insoluble.—On addition of hydro- chloric acid to the aqueous solution : no change.—On addition of caustic soda to the aqueous solution: colour becomes redder and duller.—In cone. sulphuric acid: bluish green solution, pure blue on dilution with water.—Dyes: unmordanted cotton a pure blue from an alkaline bath. Appearance of dyestuff: grayish black powder.—In water: bluish violet solution.—In alcohol: slightly soluble.—On addition of hydrochloric acid to the aqueous solution ; blue precipitate.— On addition of caustic soda: solution becomes red.—In conc. sulphuric acid: greenish blue solution, dark reddish blue pre- cipitate on dilution with water.—Dyes ; unmordanted cotton blue. Appearance of dyestuff: dark brownish red powder.—In water : red solution.—In alcohol: red solution.—On addition of hydro- chloric acid to the aqueous solution: brown precipitate.—On addition of caustic soda to the aqueous solution: red colour.— In cone. sulphuric acid : violet solution, on dilution with water a dark reddish brown precipitate.—Dyes: unmordanted cotton brown, Appearance of dyestuff: brown powder.—In water: red solution. —In alcohol; brown solution.—On addition of hydrochloric acid to the aqueous solution: brown precipitate.—On addition of caustic soda to the aqueous solution: red colour.—JIn conc. sulphuric acid : reddish violet solution ; dark reddish brown pre- cipitate on dilution with water.—Dyes: unmordanted cotton brown. Appearance of dyestuff: brownish black powder.—In water: reddish brown solution.—In alcohol : partially soluble.—On addi- tion of hydrochloric acid to the aqueous solution: brown pre- cipitate.—On addition of caustic soda to the aqueous solution : brown flocculent precipitate (if the solution is strong).—In conc. sulphuric acid: violet brown solution; on dilution with water pure violet, on further dilution, a brown precipitate. — Dyes: unmordanted cotton yellowish brown from a neutral salt bath. Year of Discoverer. Patents. Diazo Compound _poaes Discovery. Literature. 1 mol. 2 mols. 1885, C. DuIsBERG. dianisidine, naphthionic Fr. Bayer & Co. acid. Eng. Pat. 14424°* (amended). Ger. Pat. 38802®, 1 mol. 2 mols. 1891, M. HorrmMann. diphenetidine. amido- L. CassELLA & Co. naphthol-di- Eng. Pat. 1742%, sulphonic acid H. (in alkaline solution). 1 mol. 2 mols. 1889. |M. Unricn and C. Duisperc. dianisidine. | dioxynaphtha- Fr. Bayer & Co. lene-mono- Eng. Pat. 14424®° (amended). sulphonic acid Ger. Pat. app. F. 4295%, (1:8: 4). Naphthionic Diphenyl- 1888. STRASBURGER, acid. disazo- S. PFAFF. resorcinol- ACTIENGESELLSOHAFT FUR salicylic acid ANILINFABRIKATION, (Cloth Orange). Eng. Pat. 10653°°. Am. Pat. 399581. Ger. Pat. 462388, and addn. to 465018, Sulphanilic Dipheny]l- 1888. STRASBURGER. acid. disazo- S. PFAFF. resorcinol- ACTIENGESELLSCHAFT FUR salicylic acid ANILINFABRIKATION. (Cloth Orange). Eng. Pat. 10653°8, Am. Pat. 399581. Ger. Pat. 4623888, and addn. to 46501®. Sulphanilic Bismarek 1887. M. HERZBERG. acid, Brown. Fr. Bayer & Co. Eng. Pat. 16493°7. Ger. Pat. 46804%”. Naphthionic Bismarck 1887. M. Herzperc. acid. Brown. Fr. Bayer & Co. Eng. Pat. 1649387. Ger. Pat, 4680487, Appearance of dyestuff: brownish black powder.—In water : reddish brown solution.—In alcohol : partially soluble.—On addi- tion of hydrochloric acid to aqueous solution: brown pre- cipitate.—In conc. sulphuric acid: dull violet solution; brown precipitate on dilution with water.—Dyes: unmordanted cotton brown from a neutral salt bath. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. — a a Ee Se en a ee 243| Catechu Brown | Hydrochloride of Ce NC [fNeG [A.] ee ee ee C.H,4[3] NH i-amido-benzene-azo- 68 2 m-phenylene diamine. ae a “ ae ae haa}s H, [3] NH, OH, { 3] -N=N-[4] BES Mean C,H, [3] NH, [1] NH, 244; Hessian Brown Sodium salt of — | C.,H,,N,0,.S,Na, CH, [4]SO,Na BB. [L.] dipheny1-disazo-bi- ne es Ame N-[4] [1] 0H resorcinol-azo- NEN C,H, aa gt : C,H, [4] - N-[2] [3] OH acid. C,H, [4]-— N=N -[2] O,H, [1]0H CH [1]-N=N-[4] 2\[3]OH 4\[4]SO,Na 4 245| Hessian Brown bier ae Cr Hog Naso Org as CH ie SO,Na . MM. [¥.] renoveinid stat ARN " BS Bite H ia oh benzene-sulphonic O,H Aisi CH, =N—[2]J © *\ (2) OH acid. yee 3] CH, 6 3\ [4] - N= N - [2] OH, [1] 0H OH, f1]-N=N-[4] 2\(3] OH 4\ [4] SO,Na 246 | Benzo Black Blue Sodium salt of Oe tls NO 1]0H disulpho-diphenyl 4]SONa, disazo-sulpho- a-naphthol- a-naphthalene-azo- a-naphthol-sulphonic acid, S,Na G. [By.] aaa Are N[4]C,,H,[1]N = N[210,.H, : 1]0H dul tSe SICA 247 | Benzo Black Blue R. [By.] Sodium salt of CAHN gO elias ditolyl-disazo-sulpho- SABO” SB ved afagee a-naphthol- ; a-naphthalene-azo- a-naphthol-sulphonic C,H acid. s[3] CH, UL] N N[4]ygH, (1]N «N[2]C,0H1,{} : [1 s{[N:N 1 Colts] $0,Na 1]0H . 4]SO,Na| — eee a ooo CygH4N,O,;SNa, [1] 0H 4]CO,Na C,H, [4]N : N[4]C,,H, [1] N: N [2] C,H, ee Sodium salt of diphenyl-disazo- salicylic-acid- a-naphthalene-azo- a-naphthol- p-sulphonic acid. 248 Benzo Gray. ae OH, [4]: N [2] CoHs{ Hy fijoH | 4] SO,Na} 249} Azo-fuchsine B. Sodium salt of C,,H,,N,0,SNa [1] OH [ By. ] toluene-azo-dioxy- C,H, (CH,) - N=N—C,,H,, [8] OH naphthalene-mono- [4] SO,Na sulphonic acid. PtLo 4 Method of Preparation. Year of Discovery. Discoverer. Patents. Literature. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. 1887. H. KupFERBERG. ACTIENGESELLSCHAFT FUR ANILINFABRIKATION, Ger. Pat. 46375%", Appearance of dyestuff: dark brown powder.—In water: brown solution.—In alcohol: brown solution.—On addition of hydro- chloric acid to the aqueous solution : dark brown precipitate.— On addition of caustic soda to the aqueous solution: dark brown precipitate.—In conc. sulphuric acid: blackish brown solution; on dilution becoming red, then brown, and _ finally giving a brown precipitate.—Dyes : unmordanted cotton brown. — ra saa cand Combined with 1 mol. 2 mols. Bismarck phenylene Brown. diamine. 1 mol. 2 mols. benzidine. |sulpho-benzene- azo-resorcinol (Resorcin Yellow, No. 71) | 1 mol. 2 mols. tolidine. sulpho-benzene- azo-resorcinol | (Resorcin Yellow, No. 71). 1889. F. BENDER. A. LronHarpt & Co. Ger. Pat. appl. L. 5179. F, BENDER. A. LEONHARDT & Co. Ger. Pat. appl. L. 5179. 1887. R. Laven & M. Kaun. Fr. Bayer & Co. Ger. Pat. 4477987, Appearance of dyestuff: blackish brown powder.—In water : brown solution.—In alcohol: sparingly soluble.—On addition of hydro- chloric acid to the aqueous solution: brown precipitate.—On addition of caustic soda: solution becomes deep red.—In conc. sulphuric acid: violet black solution; brown precipitate on dilution with water,—Dyes ; unmordanted cotton brown. Appearance of dyestuff : brown powder.—In water : brown solution. —In alcohol: sparingly soluble.—On addition of hydrochloric acid to the aqueous solution : brown precipitate.—On addition of caustic soda to the aqueous solution: reddish brown colour.— In conc, sulphuric acid : violet black solution ; brown precipitate on dilution with water.—Dyes : unmordanted cotton brown. Appearance of dyestuff: black powder.—In water: blue black solution.—In alcohol: insoluble.—On addition of hydrochloric acid to the aqueous solution: black blue precipitate. —On addition of caustic soda: solution becomes blue.—In cone. sulphuric acid : blackish green solution ; blackish blue precipitate on dilution with water.—Dyes: unmordanted cotton black blue shades from an alkaline bath. . : 1 mol. 2 mols. disulpho- a-naphthol- diphenyl- | monosulphonic _ |disazo-mono-a-| acid NW. _ jnaphthylamine. | 1 mol. 2 mols. | ditolyl-disazo- | a-naphthol- a-naphthyl- | monosulphonic amine. acid NW. Dipheny]l- a-naphthol- 7 disazo-a- monosulphonic _ |naphthylamine-| acid NW. ¢ salicylic acid. R. Lavcn. Fr. BAYER & Co. Eng. Pat. 16484°7, Am. Pat. 440639%, Fr. ee sae ‘ ol. 40, Fol. 73. peth ) heei od fol Gi, Ital. Pat. Fol. 22, No, 24052 of 1888, Span. Pat. Fol. 365/8665 of 1888. 1890. Rk. Lavcu. Fr. BAYER & Co. Eng. Pat. 13235, Ger. Pat. appl. F. 4870. Appearance of dyestuff: grayish black powder.—In water : bluish violet solution.—In alcohol: violet solution.—On addition of hydrochloric acid to the aqueous solution: violet precipitate. —In cone. sulphuric acid : blue solution ; bluish violet precipitate on dilution with water.—Dyes: unmordanted cotton dark bluish violet from a soap bath. ; Appearance of dyestuff: grayish black powder.—In water : bordeaux brown solution. —On addition of hydrochloric acid to the aqueous solution: black precipitate.—On addition of caustic soda : no change.—In cone. sulphuric acid: blue solution; black precipitate on dilution with water.—Dyes: unmordanted cotton gray. eee | ee Toluidine. (1 :8)-dioxy- naphthalene- monosulphonic acid Sch. 1889, M. Uuricu & C. DuIsBerc. Fr. BAYER & Co. Eng. Pat. 18517. Ger. Pat. 54116°, Appearance of dyestuff : blackish brown powder.—In water : bluish red solution.—On addition of hydrochloric acid to the aqueous solution : partial precipitation of the colour as a red brown pre- cipitate.—On addition of caustic soda to the aqueous solution : colour becomes bluer.—In cone. sulphuric acid: violet solution ; bluish red on dilution with water.—Dyes: wool magenta red from an acid bath. 251 Commercial Name. Scientific Name. Azo-fuchsine G. [By.] 255 Naphthol Blue Black. [C.] Diamond Yellow G. [By.] Diamond Yellow R, [By.] Commercial Name. Dinitrosoresorcin. Fast Green. Dark Green. [B.] Chlorin. [D.H.] Russian Green. [L. ] Fast Myrtle Green. Alsace Green. Gambine R. [H.] Gambine Y. [H] Alsace Green J. Sodium salt of p-sulpho-benzene-azo- dioxy-naphthalene- sulphonic acid. Sodium salt of p-nitro-benzene-azo- disulpho-amido- naphthol-azo-benzene. Sodium salt of m-carboxy-benzene- azo-salicylic acid. Sodium salt of o-carboxy-benzene- azo-salicylic acid. Scientific Name. Empirical Formula. | Constitutional Formula. Ci gH i pN.8,0,Na, CoH 4N,O95,Nay Cy ,H,)N,0; C,,H,)N,0 5 Empirical Formula. Dinitroso-resorcinol. (Dioximidoquinone. ) 6-Nitroso-a-naphthol. (Naphthoquinone- oxim.) a-Nitroso-8-naphthol (8-Naphtho-quinone- a-Oxim. ) C,H,N,0, Cj )H,;NO, C,,H,NO, CoH [4] SO,Na [1] OH flj-N=N- cut OH [4] SO,Na onlin le C,H; -N =N> Cros [3] SO,Na [6]SO,Na | § 1 [3] CO,Na | CHL Fy -N=N - [4] C,H, - C0,Na 2 ([2]CO,Na Coley 11] -N-Ne [4] C,H; ue CO,Ne V. NITROSO AND [1] CO - C=NOH C,H, Constitutional Formula. [1] 0 [2] NOH 2) [3] 0 [4] NOH C,H [2] CH =CH 256 | i C(NOH)-CO C.H 4 [2] CH=CH re SD, [eaten «| Method of Preparation. Shade and Dyeing Properties. red solution.—On addition of hydrochloric acid to the aqueous solution: colour becomes yellower.—On addition of caustic soda: colour becomes bluer.—In conc. sulphuric acid: violet solution; bluish red on dilution.—Dyes: wool magenta red from solution.—In alcohol: tolerably soluble.—On addition of hydro- chloric acid to the aqueous solution: blue precipitate.—On addition of caustic soda: no change. — After reduction with zinc dust: the colour returns on paper.—In conc. sulphuric acid: green solution: blue precipitate on dilution.—Dyes : wool soluble with yellow colour, easily in presence of sodium carbonate or acetate.—In conc. sulphuric acid: reddish yellow solution, yellow gelatinous precipitate on dilution with water.—Dyes: Year of Discoverer. Patents. Behaviour with Reagents. : Discovery. Literature. Method of Employment. Diazo Compound | Combined with sf a Sulphanilic (1: 8)-dioxy- 1889, M. Unricu & C. Dursgerc. | APpearance of dyestuff: reddish brown powder.—In water : bluish acid, naphthalene- Fr. BAYER & Co, monosulphonic Eng. Pat. 18517. acid Sch. Ger. Pat. 54116®, an acid bath. 1 mol. 1 mol. 1891, M. HorrMann. Appearance of dyestuff: dark powder.—In water: dark blue p-nitraniline (in| (1 : 8)-amido- L. CAssELLA & Co. acid solution) | naphthol-di- Eng. Pat. 69729. and 1 mol. sulphonic aniline (in acid H. alkaline solution). a fast black from an alkaline bath. m-Amido- Salicylic acid. 1889. Rh. Laucn & C. Kreke er, | Appearance of dyestuff: grayish yellow paste.—In water : sparingly benzoic acid. Fr. Bayer & Co. Eng. Pat. 829999, Ger. Pat. appl. F. 4488. chrome mordanted wool greenish yellow. o-Amido- Salicylic acid. 1889. R. Lavon & C. KREKELER. benzoic acid. ISONITROSO COLOURS. Fr. BAyER & Co. Eng. Pat. 8299°%, Ger. Pat. appl. I. 4488. Appearance of dyestuff: brown paste.—In water : sparingly soluble with yellow colour, easily in presence of sodium carbonate or acetate. —In conc. sulphuric acid: reddish yellow solution ; brownish yellow precipitate on dilution with water.—Dyes: chrome mordanted wool reddish yellow. Method of Preparation. Action of nitrous acid upon resorcinol. Action of nitrous acid upon a-naphthol. Year of Discovery. 1875. Action of nitrous acid upon B-naphthol. 1875. Discoverer, Patents. Behaviour with Reagents. Shade and Dyeing Properties. Literature. Method of Employment. Firz. Appearance of dyestuff: grayish brown powder.—In water: Ber. (1875) 8, 631. GOLDSCHMIDT & STRAUSS. Ber. (1887) 20, 1607. KOsTANECKI. Ber. (1887) 20, 3137. J. Soc. Chem. Ind. 1890, 1126. sparingly soluble cold, more easily hot.—In dilute caustic soda: soluble.—On heating the powder: it deflagrates.—Dyes: iron- mordanted fabrics green. Fucus. Ber. (1875) 8, 625, 1026. WoRMS. Ber. (1882) 15, 1816. GOLDSCHMIDT. Ber. (1884) 17, 215, 801. GOLDSCHMIDT & SCHMIDT. Ber. (1884) 17, 2065. M. ILINSKI. Ber. (1884) 17, 2589. R. Henriques & M. ILINSKI. Ber. (1885) 18, 706. KosTANECKI. Ber. (1887) 20, 3147. J. Soe. Chem. Ind. 1890, 1126. Appearance of dyestuff: greenish yellow paste.—In water : slightly soluble with a yellow colour.—In alcohol: yellow solution.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda: clear yellow solution.— In conc. sulphuric acid: reddish brown solution; on dilution with water, yellow solution and brown flocculent precipitate.— Dyes: iron-mordanted fabrics green. FUCHS. Ber. (1875) 8, 1026. STENHOUSE & GROVES, Ann. (1877) 189, 145. H. KOHLER. Ger. Pat. 25469® (lapsed). Ber. (1883) 16, 3080. R. Henriques & M. ILINskK!. Ber. (1885) 18, 704. KosTANECKI. Ber. (1887) 20, 3147. J. Soc. Chem. Ind. 1890, 1126. R Appearance of dyestuff: olive green paste.—In water: slightly soluble with a yellow colour.—In alcohol : reddish yellow solution. —On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda to the aqueous solution: greenish yellow fluorescence.—In conc. sulphuric acid: dark brown solution ; flocculent precipitate on dilution with water.— Dyes: iron-mordanted fabrics green. No. 257 Commercial Name. Dioxine. [L.] Naphthol Green B. eeLy y) Scientific Name. Empirical Formula. Constitutional Formula. Mononitroso-dioxy- naphthalene (8-oxy- naphthaquinone- oxim. ) C, H,NO, Ferrous sodium salt of (C,)H,)N,O,)S,FeNa, [1] © (NOH)-CO Cols) ro] CH=CH [5] OH [C.] nitroso-8-naphthol- 8-mono-sulphonic acid. No.| Commercial Name. Scientific Name. Empirical Formula. 259| Alizarine Yellow | Trioxybenzophenone. Cretlsos A. [B.] 260| Alizarine Yellow | Gallacetophenone. C,H,0, C. [B.] (trioxyacetophenone. ) 261 Styrogallol. o-Dioxyanthra- C,,H,9; (Not in commerce. ) coumarin. 262} Anthracene Dibromodioxy- C,H ,Br,0;, Yellow. 6-methyl-coumarine. i [By.] C [1] NO——Fe J O ON [1] 0 out [6] SO,Na Na0,S [6] VI. OXYKETONE Constitutional Formula. [1] 0H C,H, - CO - C,H, [2] OH [3] OH [1] OH J CH, - CO- C,H,4 [2] OH f [3] OH ad coumarin with bromine. Fr. BAyver & Co. Eng. Pat. 8411. Ger. Pat. 529278, ; Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties, Method of Preparation. Discovery. Literature Method of inploymeht § trop Action of nitrous acid upon 1889. F, BENDER. Appearance of dyestuff: red paste.—In water: insoluble.—In (2 :7)-dioxynaphthalene. A, LEoNHARDT & Co. alcohol : yellowish red solution.—In cone, sulphuric acid: green Eng. Pats. 1722389 & 1423089, solution ; red precipitate on dilution with water.—Dyes: bright Ger. Pat. 5520489, green or brown shades on metallic mordants. Action of nitrous acid upon 1883. Orto HorrMANN. Appearance of dyestuff: dark green powder.—In water: yellowish 8-naphthol-mono-sulphonic Ber. (1885) 18, 46. green solution.—On addition of hydrochloric acid to the aqueous acid S and conversion into FRANKFURTER ANILIN- solution: no change.—On addition of caustic soda to the the ferrous sodium salt. FARBEN FABRIK GANS & Co. aqueous solution: colour becomes bluish green.—In conc. Eng. Pat. 22695 sulphuric acid: yellowish brown solution; yellow solution on Am, Pat. 316036. dilution with water, which gives a precipitate of Prussian blue on Ger. Pat. 28065%4, adding potassium ferro- and ferri-cyanide.—On ignition: leaves a & addn. 2890154, residue of iron sulphide.—Dyes: wool green from an acid bath J. Soc. Chem. Ind. (1885) 4, 204 ; containing an iron salt. (1890) 9, 1126. Ding. Pol. J. 254 [4], 184. COLOURS. and ofibreparaticn Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. P c Discovery. Literature. Method of Employment. Condensation of benzoic acid 1889. R. Bown. Appearance of dyestuff: grayish yellow paste.—In boiling water : or benzotrichloride with Bap. ANIL. & Sopa soluble. —On addition of hydrochloric acid: no change.—On pyrogallol. FABRIK. addition of caustic soda: deep yellow solution which quickly Eng. Pats. 8373% ; 942859 ; changes from formation of a green oxidation product.—In conc. 100952, sulphuric acid: yellow solution; white precipitate on dilution Am. Pat. 19828189, with water.—Dyes: cotton mordanted with alumina and lime a Ger. Pats. 49149 ; 50450® ; fast golden yellow. Used for printing. 504518 ; 54661%. Fr, Pat. 1982819. A. EICHENGRUN. Ann. 269, 295. J. Soe. Chem. Ind. 1893, 35. Condensation of acetic acid 1881. Nencxi & SIEBERT. Appearance of dyestuff: yellowish or white flakes or yellowish with pyrogallol in presence of Jour. Pr. Chem. 23, 147 & 538. white paste.—In hot water: easily soluble.—In alcohol: easily zine chloride. Bap, ANIL. & SopA soluble.—In aqueous caustic soda : soluble with a brown colour, FABRIK. which gets darker on exposure to air.—In conc. sulphuric acid : Eng. Pats. 837389 and 942989, light yellow solution.— Dyes: cotton mordanted with alumina Am. Pats. 415088%; yellow, with chromium brown, and with iron black. 443402 ; 4522109, Ger. Pats. 491498 & 5023859. Condensation of cinnamic acid 1886. P, Jus: Appearance of dyestuff: light yellow paste, or yellow powder of with gallic acid in presence of E. JACOBSEN. m.p. 350° C.—In water : insoluble.—In alcohol: sparingly soluble. sulphuric acid. Ger. Pat. 40375%5. —In aqueous caustic soda: green solution which on warming E. JAcoBsEN and P. Juuivs. becomes first violet and then red.—In cone. sulphuric acid: Ber. (1887) 20, 2588. yellowish red colour; yellow precipitate on dilution with water. v. KosTANKCKI. —Dyes: fabrics mordanted with alumina orange yellow. Ber. (1887) 20, 3143. Treatment of dioxy-8-methyl- 1889. R. E. Scumipr. Appearance of dyestuff: nearly white paste.—In water : sparingly soluble.—In aqueous caustic soda: brownish yellow solution from which acids reprecipitate it as a white flocculent precipitate. —In conc. sulphuric acid: pale brownish solution.— Dyes: chrome mordanted wool greenish yellow. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 263] Alizarine Black | Sodium bisulphite C,)H,SO,Na C,)H,(OH),O, + NaHSO, S. [B] ee of rater Naphthazarine 8, |°“"" sa ie 264| Galloflavine. [B.] C)3H,0, (?) 265 |Alizarine V 1. [B.]} « 8-Dioxyanthra- C,,H,0, Lt Alizarine No. I. SEE ds [6] OH [M.] [N.] CH, CoH Ate OH Alizarine Te. [By.] [2] Alizarine V. [J.] Alizarine Ta. [L. & S] 266, Alizarine R G. ‘ OUT: e CyH,0. i] and G il. [ B.] xyantnhranlavic acid. [6] OH Alizarine S D G. BOT eae ce sie OH [M.] [2] Alizarine X. [By.] Alizarine 5 R D. [Z.] Alizarine No. 10. LW.) Alizarine F A. [L. & S.J 267| Alizarine S X. ye Aa aot C,,H,O, i and G D. [B.] cee oe ieee [6] OH Alizarine RX. {i.] O*¥#soanthraflavic HHO [5] Cy

CoH aL OH Alizarine $ X. [2] extra. [By.] Alizarine 3 R F. [Z.] Alizarine 8 X. [N.] Alizarine R F. [L. & S.] Method of Preparation. Action of zine and cone. sulphuric acid or of sulphuric anhydride and flowers of sul- phur upon dinitronaphthalene and treatment of the dioxynaph- thoquinone formed with sodium hydric sulphite. Moderate oxidation of gallic acid in aqueous or alcoholic alkaline solution by means of air. Fusion of anthraquinone-mono- sulphonic acid with caustic alkalies and potassium chlorate. Year of Discovery. Discoverer. Patents. Literature. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. 1861. Z. RovssIn. Jour. Pr. Chem. 84, 181. C. LIEBERMANN. Ber. (1870) 3, 905. Ann. (1872) 162, 328, 1887. Bap. Anin. & Sopa FABRIK. Eng. Pat. 783397. Am. Pats. 368054®7 & 87915088. Ger. Pat. 4151887. Fr. Pat. 182962°7. R. Boun (bisulphite-comp. ) 1886. R. Bown. Bap. ANIL. & SoDA FABRIK. Eng. Pat. 6413°6, Am. Pat. 348618. Ger. Pat. 3793488, Fr. Pat. 1758358, R. Bown and C. GRABE. Ber. (1887) 20, 2327. Ding. Pol. J. 263, 205. J. Soc. Chem. Ind, 1887, 285, 437, 722. 1826. RosiquEer & CoLin. (from Mailder). 1868. Ber. (1869) 2, 14 & 232, Ann. Suppl. 7, 257. Ann, 160, 121. Eng. Pat. 3850%, Am. Pat. 95465, H. Caro, C. GRAEBE & C, LIEBERMANN. (from anthraquinone- sulphonic acid.) Eng. Pat. 1936. Am. Pat. 1535386. W. H. PERKIN. Eng. Pat. 1948. Ber. (1876) 9, 281. J. LEVINSTEIN. J. Soe. Chem. Ind. 1883, 213. 1869. C. GRAEBE & C, LIEBERMANN. (from dibromanthraquinone) Appearance of dyestuff: black paste.—In water: insoluble cold, witn a reddish brown colour on boiling.—In alcohol: yellowish brown solution with green fluorescence.—On addition of hydro- chloric acid to the aqueous solution: brownish red colour.—On addition of caustic soda: beautiful blue solution.—In conc. sulphuric acid : dull yellowish green solution, on heating becoming carmine red with evolution of sulphurous acid.—On dilution with water : brownish solution and black precipitate.—Dyes: chrome mordanted wool black; gives a black when printed on cotton with a chromium mordant. Appearance of dyestuff: greenish yellow paste.—In water: in- soluble.—In boiling alcohol: slightly soluble with light yellow colour and slight greenish fluorescence.—On addition of hydro- chloric acid to the paste diluted with water : hardly any change, colour rather brighter.—On addition of caustic soda: yellowish brown solution.—In conc. sulphuric acid: reddish yellow solu- tion, grayish white precipitate on dilution with water.—Dyes: chrome mordanted wool yellow fast to light and soap. Gives a greenish yellow colour when printed on cotton with a chromium mordant. Appearance of dyestuff: ochre yellow paste.—In water: insoluble. —In alcohol: insoluble cold, soluble on boiling with a yellowish red colour.—On addition of hydrochloric acid to the diluted paste : no change.—On addition of caustic soda to the diluted paste : violet solution.—In conc. sulphuric acid: deep yellowish red solution ; orange yellow precipitate on dilution with water.— Dyes: cotton mordanted with alumina scarlet red, with tin bluish red, with iron violet, and with chromium puce brown. Employed for dyeing “‘ Turkey Red” upon cotton mordanted with “‘sulphated oil” and alumina. Wool is mordanted with cream of tartar and alum, or with cream of tartar and potassium bichromate. Fusion of anthraquinone-a- disulphonic acid with caustic soda and potassium chlorate. Fusion of anthraquinone-6- disulphonie acid with caustic soda and potassium chlorate. E. Scounck & H. Romer. Ber. 9, 679; 10, 1821. H. Caro. Ber. 9, 682. 1876. Appearance of dyestuff: brownish yellow paste.—In water: in- soluble cold, very sparingly hot.—In aqueous caustic soda: violet solution. —In aqueous ammonia: brown solution.—In conc. sulphuric acid: reddish brown solution; orange. yellow precipitate on dilution with water.—Dyes: cotton mordanted with alumina red, W. H. PerKin. Jahresber. 1873, 450. G. AUERBACH. Jahresber. 1874, 488. Ber. (1876) 9, 682. 1873. Appearance of dyestuff: brownish yellow paste.—In water: in- soluble cold, very sparingly boiling—On addition of caustic soda: bluish violet solution.—In aqueous ammonia: reddish violet solution.—_In cone. sulphuric acid: cherry red solution ; orange yellow precipitate on dilution with water.—Dyes : cotton mordanted with alumina red. pone. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 268 Purpurine. Trioxyanthraquinone. C,,H,0, [1] [6] OH [2] [By] 0,8, Osc 1 [4] 0 Alizarine No. 6. i On I M] fq) 269 |Anthracene Brown.) Trioxyanthraquinone. C,,H,0, [1] [6] OH [B] (AL) [By.] CH, OOSc a 5] 0n Anthragallol. 6~4 “C07 GF [21 [4] OH 270 Alizarine Tetraoxyanthra- Cape RG? Hig ae uinone. O O Bordeaux B. [By.| 2 © Oe C O Wee 271| Alizarine Cyanine | Chiefly a penta- C,,H,0, 0 R. [By.] oxyanthraquinone. CG 272 | Alizarine Cyanine G.* [By.] Imide of the tri- or tetra-oxy-anthra- diquinone. 973| Alizarine Orange. | -Nitroalizarine. C,,H,NO, [1] [6] OH Alizarine Orange CO A. [B] [0] cae >Cat es Alizarine O R. [By.] ~ [4] NO, Alizarine O G. [By. | Alizarine N. [L. & S.] 274| Alizarine Red S. [B.] Alizarine W S. [M.] Alizarine Powder W. [By.] Alizarine W § 1. [L. & S.J Alizarine Carmine. Sodium salt of alizarine-mono- sulphonic acid. * Anthracene Blue [B.], a derivative of hexaoxyanthraquinone, is obtained by the action of fuming sulphuric C,,H,0,8Na CO Os eesti 6) [2] [6] OH [5] OH SO,Na : Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Method of Preparation. Discovery. Literature. Method of Emplowtient ener Oxidation of alizarine with 1826. Ropiauer & Contin. Appearance of dyestuff: reddish brown paste.—In water : insoluble manganese dioxide or arsenic (from -madder) cold, slightly on boiling.—In aqueous caustic soda or ammonia: acid. Bull. de Mulhouse (1826) 1, 146. magenta red solution.—In conc. sulphuric acid: reddish yellow 1874. F. pr LALANDE. solution; reddish brown precipitate on dilution with water.— (by sae alizarine) Dyes: cotton mordanted with alumina red, with chromium red- er. (1874) 7, 1545. dish brown. H. Cano. (from a-nitroalizarine and sulphuric acid) Ann. (1880) 201, 353. (a) Heating gallic acid with 1877. C. SEUBERLICH. Appearance of dyestuff: dark brown paste.—In water: insoluble. benzoic acid and sulphuric acid. Ber. (1877) 10, 38. —In alcohol: yellow solution.—On addition of hydrochloric acid (b) Heating gallic acid with G. AUERBACH. to the diluted paste : no change.—On addition of caustic soda phthalic anhydride and zine Chem. Ztg. 1882, 910. to the diluted paste : greenish blue solution.—In conc. sulphuric chloride. R. Bourcarr. acid: brownish red solution; brown precipitate on dilution with J. Soc. Chem. Ind. (1884) 3, 141. ae ‘ ; : Ban Awa. & Sony water.—Dyes: cotton mordanted with chromium brown, FABRIK. Oxidation of alizarine with 1890. R. BE. Scumipr. Appearance of dyestuff: brownish red paste.—In water: insoluble. fuming sulphuric acid (high Jour, Pr. Chem. 438, 237 2 In aqueous caustic soda: reddish violet solution.—In conc. percentage of anhydride) and ie Oe Chem. Ind. 1891, 536. sulphuric acid: bluish violet solution ; brownish red precipitate saponification of the sulphuric- Fr. EA ee Co. eae on dilution with water.—Dyes: wool mordanted with alumina ether of the tetraoxyanthra- King. pas, 8725 ie 1271 2 3 bordeaux, with chromium dark violet blue, quinone which is first formed. W712 ee 4871". 228; L Oxidation of alizarine-bordeaux 1890. R. E. Soumipr. Appearance of dyestuff: dark brown paste.—In water: insoluble. in sulphuric acid solution with Joust, ES eee. Sere p —In glacial acetic acid : yellowish red solution with green fiuor- manganese dioxide, and heating . rh ey mice G. escence.—In conc. sulphuric acid: blue solution with red fluor- the intermediate sulphuric ether En es 197159 ; 177199 , escence.—In aqueous caustic soda : blue solution. —Dyes : wool with dilute acid. g 1872 990 - 487191 ; mordanted with alumina violet, with chromium blue. Cl ? . Treatment of alizarine-cyanine 1890. R, Ei. Scumrpr. Appearance of dyestuff: black paste.—In water: insoluble.—In R or its sulphuric ether with ApS Chem. 43, 245 3 alcohol : blue violet solution.—In aqueous caustic soda or air and ammonia. ee eee ae?) oot. ammonia : greenish blue solution.—In conc. sulphuric acid : red < Fr. Bayer & Co. solution.— Dyes: wool mordanted with alumina blue, with Eng. Pisce age: ag7 1) chromium bluish green ; the colours are fast to milling. Action of nitric acid upon 1874. STROBEL. Appearance of dyestuff: brownish yellow paste.—In water: in- alizarine dissolved in nitro- H. Caro. soluble.—In aqueous sodium carbonate : magenta red solution. benzene. Eng. Pat. 122976, —With zinc dust and caustic soda: the red solution becomes Am. Pat. 18603277. yellowish brown; on exposure of the reduced solution to air it Ber. (1877) 10, 1760. turns blue.—In cone. sulphuric acid: yellowish brown solution ; A. ROSENSTIEHL. light yellow precipitate on dilution with water.—Dyes: cotton Comp. rend. 82, 1455; 83, 73. mordanted with alumina orange, with iron reddish violet, and Ann. Madera ae 519. with chromium reddish brown. Ber. (1879) 12, 583 & 1008. Action of cone. sulphuric acid ieyale C. GRAEBE & Appearance of dyestuff: orange yellow powder.—In water : easily upon alizarine. C. LIEBERMANN. soluble with yellowish red colour.—In alcohol: yellow solution. Ann. (1871) 160, 144. —On addition of hydrochloric acid to the aqueous solution : 1876. E. ULLRICH. colour becomes light yellow.—On addition of caustic soda to the 1878. H. v. PERGER. aqueous solution: colour becomes violet.—In conc. sulphuric Jour. Pr. Chem. [2] 18, 174. PRZIBRAM & Co. Ger. Pat. 3565 (expired). Eng. Pats. 11177 & 8725. C. GRAEBE. Ber. (1879) 12, 571. R. E. Scumripr. Jour. Pr. Chem. 48, 232. acid: yellowish red solution; bright yellow on dilution with water.—Dyes: wool mordanted with alumina scarlet red, with chromium bordeaux red. acid upon dinitroanthraquinone (Eng. pats. 1958891 and 1958991 ; J. Soc. Dyers and Colorists 1893, 15), No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 275 | Alizarine Maroon.| Amidoalizarin. C,,H,O,N [B.] 276| Alizarine Blue. PERT ee C,,H,NO, 1] [4] [B)] (00) quinoline. Ae N = CH Alizarine Blue CHy COM R and G W. [By.| [2] a = CH 3 277| Alizarine Blue Sodium bisulphite | C,,H,,NO,,S,Na, OH SO,Na 8. [B.] compound of dioxy- : anthraquinone- 7) quinoline. ss sc (OH) < N = CH. a aad ; CH= du OH SO,Na 278| Alizarine Indigo | Sodium peer: Chiefly : Chiefly : . compound of penta- Blue 8. [B.] beaaatheseanee Cy,H),NO,;5,Na, OH. quinoline. Wy) Neon ( = C,H (OH). C(OHy re ‘ ile OH SO,Na 279| Alizarine Green oats of aii Chiefly - Chiefly : sodium bisulphite ‘f B18] compounds of eo and | C17Hy,NO,,S,Na, ee tetra-oxy-antha- Me CH se Rea po C,H,(0H), <“>0(0H),< Bee a eir sulphonic ‘ acids. ? re 2 C,H (OH), [B.] ; Year of Discoverer, Patents. Behaviour with Reagents. Shade and Dyeing Properties. Method of Preparation, Discovery. Literature, Method of Employment. 1885. R. Boun. Appearance of dyestuff: dark violet paste.—In water: insoluble. Bap, ANIL. & SopA —On addition of hydrochloric acid to the diluted paste: no FABRIK. change.—On addition of caustic soda to the diluted paste: ’ violet solution.—In conc. sulphuric acid: red solution.—Dyes : cotton mordanted with alumina garnet red. Action of glycerine and 1877 PRUD’ HOMME. Appearance of dyestuff: small dark blue glistening crystals.—In sulphuric acid upon B-nitro- H. Brunok. water: insoluble.—In alcohol: slightly soluble on boiling with arin. Ber. (1878) 11, 522. a blue colour.—On addition of hydrochloric acid to the hot C. GRAEBE, alcoholic solution : colour becomes yellowish red.—On addition Ber. (1878) 11, 1646. of caustic soda to the hot alcoholic solution : colour becomes Ber. (1879) 12, 1416. a beautiful green.—In conc. sulphuric acid: carmine red solu- ALB. SCHEURER. S tion ; yellowish red on dilution with water. —Dyes: fabrics Bull. de Mulhouse 1884, 327. F i Ann, 201, 333. mordanted with chromium blue, Ber. 18, 170. Action of sodium bisulphite 1881. H. Brune. Appearance of dyestuff: chocolate brown powder.—In water: upon alizarine blue. Bap. ANIL. & SopDA easily soluble, with yellowish brown colour.—In alcohol: in- FABRIK. soluble. —On addition of hydrochloric acid to the aqueous Eng. Pat. 36018. solution : colour becomes more reddish yellow.—On addition of Am. Pats. 258530; 258531 ; caustic soda to the aqueous solution: colour becomes bluish 274081. violet.—In conc. sulphuric acid: dark yellow solution; brown Ger. Pats. 176958! & 23008%2. precipitate on dilution.—Dyes : chrome mordanted fabrics blue. Fr. Pat. 1448868. H. Bruncok & C. GRAEBE. Ber. (1882) 15, 1783. Ann. (1880) 201, 333. I, LEVINSTEIN. J. Soc. Chem, Ind. 1883, 223. Action of sulphuric acid upon 1888. R. Bown. Appearance of dyestuff: brownish black paste.—In cold water: alizarine green and subsequent Bap. ANIL. & SoDA red solution ; on boiling the solution by itself or with hydrochloric treatment of the product with FABRIK. acid, alizarine-indigo blue separates out.—On addition of caustic sodium hydric sulphite. Eng. Pat. 1512188, soda: blue solution.—Dyes ; chrome mordanted wool indigo blue. Am. Pat. 39948289, Ger. Pat. 4725258, addn. to 46654. Fr. Pat. 192582 (supp.) J. Soc. Dyers & Colorists 1889, 106 ; 1893, 68. Action of sulphuric acid upon 1888. k. Bown. Appearance of dyestuff: brownish black solution.—In water: alizarine blue, and subsequent Bap. ANIL. & SopA soluble cold, on boiling alizarine green separates out.—On addition treatment of the product with FABRIK. of caustic soda : ‘violet solution.—Dyes : chrome mordanted wool sodium hydric sulphite. Eng. Pat. 14353, fast bluish green. Am, Pats. 399479 ; 399480 ; 399481 ; 401633 ; 401635. Ger. Pat. 4665488, Fr, Pat. 19258288, J. Soc. Chem. Ind. 1889, 770 ; 1890, 58; 1891, 1003. J. Soc, Dyers & Colorists 1889, 106 ; 1893, 68. Action of sulphuric acid upon 1835. RoBIQuEt. Appearance of dyestuff: brownish red powder.—In water: in- gallic acid. Ann, (1836) 19, 204. soluble-—On addition of hydrochloric acid: no change.—On addition of caustic soda: blue solution, which quickly changes in the air.—In cone. sulphuric acid : red solution.—Dyes : chrome mordanted wool brown. [ 130 VII. DIPHENYL- No. Commercial Name. Scientific Name. 281 Auramine, Auramine O. [B.] 282 Pyronine G. [L.] 283 Pyronine B. [L.] 284; Acridine Red 3 B. [L.] Hydrochloride of imido-tetramethy]- diamido-dipheny]l- methane. Hydrochloride of tetramethyldiamido- oxydiphenylearbinol. Hydrochloride of tetraethyldiamido- oxydiphenylcarbinol. Empirical Formula. C,,H,,N,C10 C,,H,,N,OC1 C,5H,,N,OCl * CCa [1] C,H,[4] N (CH3), HO-C [1] C,H,[4] N (CH), O—/1]C,H,[3] N=N[1] 0,0 | ea C,H,[4] i (CH,), [4] OH 3{[3] CO, toluidine, were prepared by A. Poirrier, C. Bardy, and Ch. Lauth (see Fr. pat. 281899; Eng. pat. 367569; Ber. 3, 807) and brought into commerce as Paris — + Cyanine [M.] is a dark blue obtained by Perse: «| Method of Preparation. Condensation of benzaldehyde with benzyl-ethyl-aniline, sulphonation of the diethyldi- benzyldiamidotriphenylmethane obtained, and oxidation of the sulphonic acid. Condensation of benzaldehyde with benzylethylaniline- sulphonic acid and oxidation of the diethyldibenzyldiamido- triphenylmethane-disulphonic acid produced. Condensation of m-nitrobenz- aldehyde with benzylethyl- aniline-sulphonic acid and oxidation of the nitrodiethyldi- a benzyldiamidotriphenyl- methane-disulphonic acid produced. Year of Discovery. 1879. 1883. 1889. Action of commercial benzyl chloride upon diphenylamine, oxidation of the product and sulphonation of the colouring- matter obtained. Condensation of m-nitrobenz- aldehyde with dimethylaniline, reduction of the m-nitro- compound to the m-amido- compound, conversion into the m-oxy-compound by treatment with nitrous acid, sulphonation of the product, and oxidation of the leuco sulphonic acid. en 1 ere ea —— = Combination of the diazo compound of m-amido-tetra- methyl-diamido-triphenyl- methane with salicylic acid, and oxidation of the product. matiéres colorantes 1876, p. 134. Green or Vert-de-Paris. oxidation of patent blue (Eng. pat. 796491), 1888. 1888. Discoverer. Patents. Literature. KOHLER. Bap. ANIL. & SODA FABRIK. Fr. BAyER & Co. P. FRIEDLANDER. Ber. 22, 588. O. MUHLHAUSER. Ding. Pol. J. 263, 249, 295. J. Soc. Chem. Ind. 1887, 433 ; 1890, 50. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: bright green dull powder.—In water: green solution.—In alcohol: soluble.-—On addition of hydro- chloric acid to the aqueous solution: colour becomes yellowish brown.—On addition of caustic soda to the aqueous solution : decolourised with formation of dull violet precipitate. —With barium chloride or picric acid: no precipitate.—In conc. sulphuric acid: yellow solution ; green on dilution with water.— Dyes: silk and wool green from an acid bath. G. Scuutrz & EK. StRENG. ACTIENGESELLSCHAFT FUR ANILINFABRIKATION. Eng. Pat. 7550°%. Ger. Pat. 5078259, Fr. Pat. 198417®, AOTIENGESELLSCHAFT FUR ANILINFABRIKATION. Eng. Pat. 7550°, Ger. Pat. 50782°®. Fr, Pat. 198417®. R. MELDOLA. J. Chem. Soc. 1882, 187. Ber. 14, 1385; 15, 1580. Brooke, SIMPson, & SPILLER. Appearance of dyestuff: dull dark green powder.—In water or alcohol: green solution.—On addition of hydrochloric acid to the aqueous solution: colour becomes brownish yellow.—On addition of caustic soda to the aqueous solution: blackish green precipitate.—With barium chloride: green precipitate.— In conc. sulphuric acid: yellow solution ; on dilution with water, yellowish red, yellowish green, and finally green.—Dyes: silk and wool green from an acid bath, Appearance of dyestuff: bluish green powder.—In water: green solution.—In alcohol: slightly soluble.-—On addition of hydro- chloric acid to the aqueous solution: bluish green precipitate.— On addition of caustic soda to the aqueous solution : becomes light green, nearly decolourised.—In cone. sulphuric acid: brown solution; yellowish green on dilution with water.—Dyes: wool green from an acid bath. Appearance of dyestuff: dark green powder.—In water: green solution.—On addition of hydrochloric acid to the aqueous solution : green precipitate.—On addition of caustic soda to the aqueous solution: colour becomes brown.—In conc. sulphuric acid : magenta red solution; green flocculent precipitate on dilu- tion with water. HERRMANN. MerrstEr, Lucius, & BRUNING. Eng. Pats. 127968 & 148228, Ger. Pats. 4638488 ; 50286® ; 4852388 ; 5029388; 504408. ULLRICH. Am. Pats. 412613; 412614 reissue 11078 ; 412615 reissue 11077. Ger. Pat. 556219, Chem. Ztg. 1889, 1702. J. Soc. Dyers and Colorists 1889, 106. O. Soust & F. RuNKEL. Fr. BAYER & Co. Eng. Pat. 3398%. Ger. Pat. 5745289, J. Soc. Chem. Ind, 1892, 31. Appearance of dyestuff: copper red or blue powder.—In water: blue solution.—In alcohol: slightly soluble.—On addition of hydrochloric acid to the aqueous solution: colour becomes green and finally yellow.—On addition of caustic soda to the aqueous solution: in the cold no change, on boiling the colour becomes violet.—In conc. sulphuric acid : yellowish solution ; deep yellow and finally green on dilution with water.—Dyes: wool greenish blue. Appearance of dyestuff: dark green paste.—In water: sparingly soluble with a green colour.—In alcohol: sparingly soluble with a green colour.—On addition of hydrochloric acid to the diluted paste: colour becomes brownish red.—On addition of caustic soda: clear solution on warming.—In conc. sulphuric acid: reddish brown solution ; reddish flocculent precipitate on dilution with water,—Dyes : chromed wool green. Dyestuffs, obtained by the action of oxidising agents upon benzylaniline, dibenzylaniline, benzyltoluidine, or dibenzyl The preparation of sulphonic acids of these dyestuffs was claimed by De Lalande (Ger. pat. 956975); cp. Eng. pat. 272179 prov. a-naphthyl-carbinol. | [1] Cy >H,[4] N (C,H,) HCl No.| Commercial Name. Scientific Name. Empirical formula. Constitutional Formula. 296| Victoria Blue Hydrochloride of C,,H.N,Cl [1] C,H,[4] N (CH,), B. [B.] [L] Ne chest C<—_[1] C,H,[4] N (CH,), riamido-diphenyl- 11C. HI41N (C.EDHCL a-naphthyl-carbinol. | [1] C,oH14] | (C,H;) | | | 297 Night Blue. Hy arosnonce ot CHa Nagel | [1] C,H,[4] N (C,H,), p-tolyltetraethyl- ae) triamido-dipheny]l- e [1] CoH, [4] N (CoH), 298| Victoria Blue Hydrochloride of C.,He NACL [1] C,H,[4] N (CH,), 4B. [B.] [2] Me pe diphenyl rjc, sH,[4] N (CH,), a-naphthyl-carbinol. | [1] C,H [4] ‘ cat} (CgH,) Cl Or [1] C,H,[4] N (CH,), C<— [1] C,H,[4] N CH,), [Loti (CH) (Ct) a 299| Para-fuchsine. Hydrochloride of C,)H,,N,C10, [1] C,H,[4] NH, pararosaniline. 6) [1] C,H,[4] NH, +4H,0 Hydrochloride of | (1) CBee triamido-triphenyl- | carbinol, fb 1a7] i Method of Preparation. Year of Discovery. Discoverer. Patents. Literature. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. (a) Action of phenyl-a-naphthyl- amine upon tetramethyl- diamido-benzophenone chloride. (b) Action of phenyl-a-naphthy]. amine upon tetramethyl- diamido-thiobenzophenone in presence of condensing agents. (c) Condensation of tetramethyl- diamidobenzhydrol with pheny]- a-naphthylamine, conversion of the leuco base into its nitros- amine, oxidation and removal of the nitroso group. Action of p-tolyl-a-naphthyl- amine upon tetraethyldiamido- benzophenone chloride. Action of methyl-phenyl- a-naphthylamine upon tetra- methyldiamido-benzophenone chloride. (a) Oxidation of a mixture of aniline and p-toluidine with arsenic acid. (0) Heating nitrobenzene and | p-nitrotoluene with aniline, p- _ |toluidine, iron, and hydrochloric acid, (c) Heating diamidodiphenyl- methane (or formaldehyde- anilide) with aniline hydro- | chloride and aniline in presence of an oxidising agent. | (da) Oxidation of triamido- _| triphenylmethane in acetone or alcoholic solution. 1883. H. Caro & A. Kern. Bap. Antu. & SopDA FABRIK. Ing. Pats. 503854 & 12022°%. Am. Pat. 29741484, Ger. Pats. 277893 & 2996254. Fr. Pat. 160090", Fr. BAYER & Co. Eng. Pat. 19062A%, M. NATHANSON & P. MULLER. Ber. (1889) 22, 1888. 1883. 1883, 1858. 1869. 1889, H. Caro & A. KERn. Bap. ANIL. & SoDA FABRIK. Eng. Pats. 5038°4 & 120228¢ Ger. Pat. 27789®. H. Caro & A. KErn. Bap, ANIL. & SoDA FABRIK. Eng. Pats. 5038%4 & 12022, Am, Pat. 3087488, Ger. Pat. 27789®. Fr. Pat. 160090%. M. NATHANSON & P. MULLER. Ber, (1889) 22, 1891. A. W. HormMann. Jahresber. 1858, 351; Jour. Pr. Chem. (1859) 77, 190 ; (1862) 87, 226. ROSENSTIEHL. Bull. de Mulhouse 36, 264; Ding. Pol. J. 181, 389. Meister, Lucius, & BRUNING. Eng. Pat. 20678°. Ger. Pat. 61146. Theory: Cano & GRAEBE. Ber. (1878) 11, 1117. EK. & O. FiscHEr. Ann. (1878) 194, 242; Ber. (1878) 11, 1079 ; (1880) 13, 2204. Methods of formation : G. SCHULTZ. Chemie des Steinkohlentheers. 2nd edit. 2, 395. O. MUHLHAUSER. Die Technik der Rosanilin- farbstoffe, Appearance of dyestuff: bronzy glistening powder.—In water: sparingly soluble cold, noderately soluble hot.—In alcohol : easily soluble to a pure blue solution.—On addition of hydrochloric acid to the aqueous solution: blue precipitate, redissolving in excess to a green, or with a large excess to a yellowish brown solu- tion.—On addition of caustic soda to the aqueous solution: dark reddish brown precipitate.—In conc. sulphuric acid: red- dish yellow solution ; becoming yellow, green, and finally blue on dilution with water.—Dyes: silk and wool blue from an acid bath; cotton either direct from an acetic acid bath or after previous mordanting with tannin and tartar emetic or with alum, Appearance of dyestuff: violet bronzy powder.—In water: bluish violet solution.—In alcohol: easily soluble. —On addition of hydrochloric acid to the aqueous solution: precipitate which dissolves in excess to a green, in a large excess to a yellowish brown solution.—On addition of caustic soda to the aqueous solution: pale reddish brown precipitate.—In conc. sulphuric acid: yellowish brown solution; becoming green and finally blue on dilution with water.—Dyes: like Victoria blue B but a greener shade, Appearance of dyestuff: bronzy glistening powder.—In hot water : bluish violet solution.—On addition of hydrochloric acid to the aqueous solution: precipitate which dissolves in excess to a green, in a large excess to a yellowish brown solution.—On addi- tion of caustic soda to the aqueous solution: violet brown pre- cipitate.—In conc. sulphuric acid: yellowish brown solution ; becoming green and finally blue on dilution with water.—Dyes : like Victoria blue B but a much redder shade, Appearance of dyestuff : cantharides-glistening crystals.—In water : sparingly soluble cold, more readily hot.—In alcohol: easily soluble to a crimson solution.—On addition of hydrochloric acid to the aqueous solution; colour becomes yellow.—On addition of caustic soda: reddish crystalline precipitate of the base,—In cone, sulphuric acid : yellow solution ; colourless on dilution with water.—Dyes: wool, silk, and leather magenta red direct, cotton after mordanting with tannin and tartar emetic. No. 300 Magenta.* [R.H.] Roseine. [B.S.S.] Fuchsine. [B.] [By.] [AL] [C.] Aniline Red. Rubine. Azaleine. Solferino. Erythrobenzin. Fuchsiacine. Harmaline. Rubianite. Commercial Name. Scientific Name. 301| Acid Magenta. [B.] Fuchsine S. [B.] [MZ] Acid Roseine. Acid Rubine. Rubine §. [4.] * New Magenta or Isorubine [M.] is the hydrochloride of tri-o-tolyl-carbinol obtained synthetically from o-toluidine and formaldehyde (Ger. pat. 5977 Acid Fuchsiune. + Mixture of hydro- chloride or acetate (rarely nitrate or sulphate) of para- rosaniline (triamido- triphenylcarbinol) and rosaniline (tri- amidodiphenyltoly1- carbinol). Mixture of the sodium or ammonium salts of the trisulphonic acids of rosaniline and pararosaniline, | Impure kinds of acid magenta come into commerce as Maroon S$ [B.], Grenat S [B.], Acid Cerise [1/.], Cardina [ 138 Empirical Formula. Hydrochlorides : C,H, ,N,C10, CopHogN C10, Acetates : CoH, N05 oo Ho3N.O, Nitrates : Cy9H, NO, Cop Ho oN 405 Sulphates : C,H. .NGSO, C, pH yoN SO, Sodiwm salts - C, 9H gN01)S3Na, C.9HygN,0))S,Na, ] Constitutional Formula. Hydrochlorides : [1] C,H,[4] NH, +4H,,0 [1] C,H, [4] NH, | [1] C,H, [4] NH,Cl and 3] CH, Me {Hee 0< iyo, H[4|NH, +4H,0 [1] C,H, [4] NH,Cl . a [4] NH. [1] CyHs S0-Na - 4] NH [1] CH EG Ne : [1] 08s £6 Na HO-C and eds HO= Ce a OH EG. aes [3] CH, [1] O,H, fe NH, O,Na phosphine, ete., come into commerce under the names 169° 7 Method of Preparation. Year of Discovery. Discoverer. Patents. Literature. (a) Oxidation of a mixture of aniline, o-toluidine and p-tolui- dine by means of arsenic acid (arsenic acid method). (b) Heating a mixture of aniline, o-toluidine, and p-toluidine, with nitrobenzene, o-nitro- toluene and p-nitrotoluene in presence of iron and hydro- chloric acid (nitrobenzol method). (c) Heating a mixture of aniline and toluidine with mercuric nitrate or chloride (not now employed). Action of fuming sulphuric acid upon magenta, 1856. 1859. 1860. 1861. 1869. 1877. NATANSON. (from aniline and ethylene chloride) Ann. (1856) 98, 297. A. W. HOFMANN. (from aniline and carbon tetrachloride) Jahresber. (1858) 353; Jour. Pr. Chem. (1859) 77, 190 ; (1862) 87, 226. VERGUIN, (from toluidine-containing aniline and stannic chloride) RENARD FRbERES ET FRANC In Lyon. Fr. Pat. of 8th April 1859. Ding. Pol. J. (1859) 154, 236 & 397. GERBER & KELLER. (from toluidine-containing aniline and mercuric nitrate) Fr. Pat. of 29th October 1859. H. MEDLOCK. (from toluidine-containing aniline and arsenic acid) Eng. Pat. of 18th January 1860. Ding. Pol. J. (1860) 158, 146. HK. C. NIcHOLSON. Eng. Pat. of 26th January 1860. GirARD & Dr LATRE. Fr. Pat. of 26th May 1860. LAURENT & CASTHELAZ. (from nitrotoluene-containing nitrobenzene, iron, and hydrochloric acid) Fr. Pat. of 10th December 1861. Wagner's Jahresber. 8, 567. CourPIER. (from nitrobenzene, nitro- toluene, aniline, toluidine, iron, and hydrochloric acid) Wagner’s Jahresber. (1869) 15, 568 ; Ber. (1878) 6, 25, 423, 1072. Methods of formation and manu- Jacture: G. ScHULTz. Chemie des Steinkohlentheers. 2nd Edit. II., 404. O. MUHLHAUSER, Technik der Rosanilinfarbstoffe. Ding. Pol. J. cen) 266, 455, 503, P. ScHoop. Ding. Pol. J. (1885) 258, 276. J. Soc. Chem. Ind. 1886, 163 ; 1888, 118. Theory ; see references under Parafuchsine. H. Caro. Bap. ANIL. & SoDA FABRIK. - Ber. (1878), 11, 1949. Eng. Pat. 37317, Am. Pat. 250201. Ger. Pat. 209677, Fr, Pat. 12272178. Reap Houiipay & Co. Am. Pat. 250247. E. JACOBSEN. Ber. (1880) 13, 294. Eng. Pat. 282879. Ger. Pat. 876479, P. ScHoopr. Chem. Zeit. 11, 572 J. Soc, Chem, Ind. 1887, 592. Behaviour with Reagents, Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff : the hydrochloride forms cantharides-glisten- ing crystals, the acetate fused green glistening lumps, the sulphate a fine green glistening crystalline powder.—In water : red solution. —In alcohol: red solution.—On addition of hydrochloric acid to the aqueous solution : yellow.—On addition of caustic soda to the aqueous solution : nearly decolourised with precipitation of the base.—In conc, sulphuric acid: yellowish brown solution, nearly colourless on dilution with water.—Dyes: silk, wool, and leather bluish red direct, cotton after having been mordanted with tannin and tartar emetic. Appearance of dyestuff: metallic green glistening granules or powder.—In water: easily soluble to a crimson solution.—In alcohol: nearly insoluble.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda to the aqueous solution : almost completely decolourised. —In cone, sulphuric acid: yellow solution; red on dilution with water. —Dyes : wool and silk red from an acid bath ; not employed for cotton, It forms a bronzy green powder, much more soluble in water, and of slightly bluer shade than ordinary magenta. Impure kinds of magenta containing Maroon, Grenat, Geranium [C.], Cerise [C.], Ponceau, etc. Red S, Acid Maroon, Grenadine, Cerise, etc. ; see Bad. Anil. & Soda Fabrik, Ger. pat. 209677 ; Ber. (1878) 11, 1949. [aa No. | Commercial Name. 302| Red Violet 4 RS. Scientific Name. Empirical Formula. Constitutional Formula. Cy9H,9N30,5,Na, Sodium salt of SO,Na dimethylrosaniline- [B] nethylrosanili [1] C,H, [3] CH, trisulphonic acid. ‘Uy 4 Be CH, a oem rhs Se ee NHCH, SO,Na ies ‘tts NH 303| Methyl Violet B, | Chiefly: C,,H,,N,Cl [1] O,H,[4] N CH,), [B.] [By.] [4] [C.] [A] Paris Violet. Direct Violet. Violet de Methyl- aniline. Dahlia. Pyoktanine.* Hydrochloride of penta- and hexa- methyl-pararos- aniline, 304 | Crystal Violet. [B.] [1] Hydrochloride of hexamethyl- pararosaniline. 30 Or Methyl Green. [By.] Paris Green. Vert Etincelle. [ Mo. ] Light Green. Vert de methyl- aniline. Vert lumiére. Double Green. [K.] Green Powder. Zine-double-chloride of heptamethyl- pararosaniline- chloride. Bronzy crystals : C,,H,)N,Cl + 8H,O Cantharides- glistening crystals : C,,H,)N,Cl C,sHsN,Cl,Zn * Under this name it is brought into commerce by E. Merck as an antiseptic ; cp. J . Stilling, C< [1] C,H,[4] N (CH,), | [1] C,H, [4] x (CH,) HCl [1] C,H,[4] N (CH). Ch] C.H,[4] N (CH,), [1] C,H,[4] N (CH,),Cl |e [1] C,H,[4] N (CH), C<—[1] C,H, [4] N (CH,),Cl + ZnCl, | [1] C,H,[4] N (CH,),Cl |" aa peer . Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Method of Preparation. Discovery. Literature. Method of Employment. 3 Action of fuming sulphuric acid 1877. H. Caro. Appearance of dyestuff: reddish violet powder.—In water : easily upon dimethylrosaniline, Bap. ANIL. & SoDA soluble with magenta red colour.—On addition of hydrochloric FABRIK. acid to the aqueous solution: no change.—On warming the Ber. (1878) 11, 1949. aqueous solution with caustic soda : colour becomes pale reddish Eng. Pat. 37317. yellow.—In conc. sulphuric acid: brownish yellow solution ; Am. Pats. 204797 & 20479878, magenta red on dilution with water.—Dyes: wool from an acid Ger. Pat. 209677. bath a bluer shade than acid-magenta. Oxidation of dimethylaniline 1861. Cu. LAUTH. Appearance of dyestuff : glistening metallic-green luinps or powder. with cupric chloride. Mon. Scien. (1861) 336. —In water : violet solution.—In alcohol or amyl alcohol : easily Porrrizr & CHAPPAT. soluble.—On addition of hydrochloric acid to the aqueous Fr. Pat. 71970%, solution : the colour turns first green then deep yellowish brown. Sah ea oe —On addition of caustic soda to the aqueous solution : brown- AL Ww HOFMANN, ; ish red coloration and precipitate.—In conc. sulphuric acid: Ber. (1873) 6, 359. yellow solution, becoming yellowish green, greenish blue, and E. & O. Fiscumr. finally violet on dilution with water.—Dyes : silk and wool violet Ber. (1878) 11, 2098 ; (1879) 12, 2350. direct, cotton after mordanting with tannin and tartar-emetic. Ann. (1878) 194, 295. O. Fiscuer & L. GERMANN. |r Ber. (1883) 16, 710. H. WICHELHAUS Ber. (1883) 16, 2005. O. Fiscoer & G. KORNER. Ber. (1883) 16, 2904; (1884) 17, 98. O. MUHLHAUSER. Ding. Pol. J. 264, 37. J. Soc, Chem, Ind. 1887, 434. (a) Action of dimethylaniline 1883. A. KERN. Appearance of dyestuff: bronzy or cantharides-glistening crystals. upon tetramethyl-diamido- (from tetramethyldiamido- —In water : violet solution.—In alcohol : soluble.-—On addition benzophenone chloride. benzhydrol) of hydrochloric acid to the aqueous solution : colour becomes (0) Direct action of carbonyl H. Caro. first blue, then green, and finally yellow.—On addition of caustic chloride in presence of zinc (from tetramethyldiamido- soda to the aqueous solution: violet precipitate. —In conc. chloride upon dimethylaniline. benzophenone) sulphuric acid : yellow solution ; becoming green, blue, and finally (c) Direct action of thiocarbonyl- GESELLSCHAFT FUR CHEM. violet, on dilution with water.—Dyes : silk and wool violet direct, chloride upon dimethylaniline. INDUSTRIE in B ASEL, and cotton after having been mordanted with tannin and tartar-emetic. (d) Condensation of tetramethyl- Bap. Antu. & SopA diamidobenzhydrol with FABRIK. dimethylaniline and oxidation Eng. Pats. 4428 ; 11030* ; of the leuco-base. 485084 ; 5038%; 1202286, Am. Pats. 290891 ; 290892 ; 290856. Ger. Pats. 260168 ; 27032% ; 277898 ; 29943%4 (addn.) ; 299625 (addn. ). Fr. Pats. 1574308 ; 16009084, | 2 KeErn & SANDOZ. Ger. Pat. 64270%. O. FiscHer & L. GERMANN. Ber. (1883) 16, 706. O. Fiscuer & G. KORNER. Ber. (1883) 16, 2904. A. W. HoFFMANN. Ber. (1885) 18, 767. J. Soc. Chem. Ind. 1885, 395. (a) Action of methyl nitrate on} 1871. Cu. Lautu & Bausieny. Appearance of dyestuff: green crystals.—In water : easily soluble methyl violet (obsolete). (from methyl violet and with a bluish green colour ; a spot of the solution dried on paper (b) Action of methyl chloride methyl nitrate) becomes violet on heating strongly.—In amyl alcohol: insoluble. upon methyl violet in amyl- Ber. (1873) 6, 825. —On addition of hydrochloric acid to the aqueous solution : alcoholic solution 1873. Monnet & REVERDIN. colour becomes reddish yellow ; on dilution with water it changes : (from methyl violet and to yellowish green.—On addition of caustic soda to the aqueous methyl chloride) solution : decolourised.—In cone. sulphuric acid : reddish yellow Mon. Scien. (1878) 124. solution; yellowish green on dilution with water.—Dyes; silk A. W. Hormann. | green from a soap bath. Ber. (1873) 6, 363. E. & O. FISCHER. Ber, (1879) 12, 2351. “ Anilinfarbstoffe als Antiseptica,” Strassburg 1890; O. Liebrich, Ther. Monatshefte 4, 344. Scientific Name. Empirical Formula. Constitutional Formula. No.| Commercial Name. 306| Todine Green.* Zine-double-chloride : of heptamethyl- Baht 7 ele rosaniline chloride. Vert lumieére. (No longer in com- merce. ) 307| Benzyl Violet. Chiefly a mixture of 308 309 310 Paris Violet 6 B. Methyl Violet 6 B. Methyl Violet 6 B extra. [A.] [C.] [17] Violet 5 B. [by.] Violet 6 B. [By.] Fast Green. [By.] Fast Green extra. [By.] Fast Green extra, bluish. [By.] Hofmann Violet. [B.S.8.] Iodine Violet. Dahlia. Primula. Red Violet 5 R extra. [B.] Violet 5 R. [By.] Violet R. [1/o.] Violet RR, [1/o.] Ethyl Violet. [B.] [2.] Ethyl Purple 6 B. 811 Ethyl Green. Methyl Green. [By.] CoH, N Cl yan. vy, [3] CH U1 Cals (LN tty, C11] C,H,[4] N (CH,),Cl + ZnCl, | [1] C,H, [4] ‘ (CH,).Cl Benzylpentamethyl- the hydrochlorides of | pararosaniline ME eet d hydrochloride : pararosaniline and y : hexamethylpara- C,,H,,N,Cl rosaniline. Sodium salt of C,H N-0.S2Na. tetramethyldibenzyl- RE Rit a pseudorosaniline- disulphonic acid. Mixture of the hydrochlorides or acetates of the mono- di-.or tri-methyl- (or ethyl)-rosanilines and pararosanilines. Hydrochloride of hexaethy]para- rosaniline. Zinc-double-chloride of ethylhexamethyl- pararosaniline- bromide. Hydrochloride of triethylrosaniline « CygHy.N,Cl Cy HyN Cl C,,H,,N.C1,Br Zn [1] CoH,[4] N (CH), C<— [1] C,H, [4] N (CH,), | (1] C,H, [4] : (CH,) (CH, - C,H,)Cl [1] O,H,[4] N (CH,), HO-C [1] C,H,[4] N (CH,), [1] CsH,[3] N (CH, - C,H, - SO,Na), Hydrochloride of triethylrosaniline : [3] CH, (11 CoH Fa] NE C,H) C [1] C,H,[4] NH (C,H;) | [1] C,H,[4] NH (C,H,)Cl [1] C,H, [4] N (0,1), C [1] C,H,[4] N (C,H;), Piaoren [1] C,H,[4] N (CH,), C<—_[1] C,H,[4] N (CH,),(C,H,)Br | [1] C,H, [4] ; (CH,),Cl * The picrate of heptamethylrosaniline-chloride at +ZnCl, | a ee rae ae ee, eer ee Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: dark green hard lumps.—In water : easily soluble with a bluish green colour ; a drop of this solution dried upon paper turns violet when strongly heated.—On addition of hydrochloric acid to the aqueous solution : colour becomes red- dish yelow.—On addition of caustic soda to the aqueous solu- tion: decolourised.—In conc. sulphuric acid: reddish yellow solution ; pale yellowish green on dilution with water.—On heat- ing with conc. sulphuric acid : evolves iodine vapours if prepared with methyl iodide.—Dyes : silk green. Appearance of dyestuff: metallic glistening lumps or powder.—The reactions are the same as those of methyl violet B. Appearance of dyestuff: dark bluish green crystalline powder. —In water: greenish blue solution.—In alcohol: soluble.—On addition of hydrochloric acid to the aqueous solution: colour becomes yellow; greenish yellow on dilution with water.—On addition of caustic soda to the aqueous solution: decolourised on warming.—In conc. sulphuric acid: yellowish red solution ; becomes nearly colourless on dilution with water, with great dilution greenish blue.—Dyes: wool bluish green from an acid bath. (a) Red shades (Red violet 5 R extra [B.]): Appearance of dyestuff: green crystalline powder.—In water: magenta red solution.—On addition of hydrochloric acid: colour becomes yellowish brown.—On addition of caustic soda: brown precipitate.—In conc. sulphuric acid : yellowish brown solution ; no change on dilution.—Dyes : wool bluish red. (b) Blue shades (Hofmann’s violet) : Appearance of dyestuff: green glistening lumps.—In water: easily soluble with bluish violet colour.—On warming with zinc dust: decolourised.—On addition of hydrochloric acid to the aqueous solution : first green then yellow.—On addition of caustic soda: brownish red precipitate—In conc. sulphuric acid: brownish yellow solution ; becomes olive-green, green, and finally blue, on dilution with water.—Dyes: wool, silk, and mordanted cotton violet. Appearance of dyestuff: green crystalline powder.—_In water: easily soluble with a violet blue colour.—On addition of hydro- chloric acid to the aqueous solution: colour becomes reddish yellow.—On addition of caustic soda to the aqueous solution : grayish violet precipitate, which on heating melts together to a brown oil leaving the solution colourless.—In conc. sulphuric acid: brownish yellow solution ; becomes green on great dilution with water.—Dyes : silk and wool bluish violet direct, cotton after mordanting with tannin and tartar-emetic, : Year of Discoverer. Patents. Method of Preparation. Discovery. Literature. Action of methyl iodide or 1866. J. Keisser. methyl chloride upon rosaniline Fr. Pat. of 18th April 1866. or upon Hofmann violet. La FucHSINE. Mon. Scien. 1867, 536. Wagner's Jahresber. (1867) 18, 597. A. W. Hormann & CO. H. Grrarp. Ber. (1869) 2, 442. H. ApPENZELLER. : Ber, (1873) 6, 965. Action of benzyl chloride upon | 1868. Cu. Laura. methyl violet. O. Fiscuer & G. Korner. Ber. (1883) 16, 2910. O. MUHLHAUSER. Ding. Pol. J. 270, 179. J. Soc. Chem. Ind. 1889, 40. Action of m-nitrobenzaldehyde | 1885. H. HAssENKAMP. upon dimethylaniline, reduction Fr. BAYER & Co. of the condensation-product, Ger. Pat. 37067®. benzylation, sulphonation, and J. Soc, Chem, Ind. 1892, 30. finally oxidation of the leuco- sulphonic acid obtained. Action of methyl (or ethyl) 1863. A. W. HorMann. chloride, bromide, or iodide Comp. rend. 54, 428 : 56, ia 1033 ; upon rosaniline and pararos- Bis Ete oo aig aniline. Chemie des Steinkohlentheers. 2nd. edit. vol. ii. p. 467. (a) Action of diethylaniline 1883. A. KERN. upon tetraethyldiamido- (from tetraethyldiamido- benzophenone chloride, benzhydrol) (b) Direct action of carbonyl H.Caro, chloride upon diethylaniline in (from tetraethyldiamido- presence of zine chloride. benzophenone chloride) GESELLSCHAFT FUR CHEM. INDUSTRIE in BASEL and Bap. Aniu. & Sopa FABRIK. Eng. Pats. 4428 ; 5038% ; 11030*4, Am. Pats. 290856 ; 290891 ; . 290892 ; 290893. Ger. Pats. 26016 ; 27032® ; 2778988 ; 2994384 (addn.) ; 2996254 (addn.). 1866, HOouuipay. Action of ethyl bromide upon methyl violet. one time appeared in commerce as Green-in-paste. Eng. Pat. of Ist May 1866. Appearance of dyestuff : moss-green crystalline powder.—In water : easily soluble with greenish blue colour.—On addition of hydro- chloric acid to the aqueous solution : colour becomes first green and then yellow.—On addition of caustic soda: decolourised.— In conc. sulphuric acid: yellowish solution ; becomes green on great dilution with water.—Dyes : wool mordanted with sodium thiosulphate and sulphuric acid or zine acetate, silk, and cotton mordanted with tannin, bluish green. [144 Constitutional Formula. [1] C,H,[4] N (CH,), [1] C,H, [4] N (CH,), [1] C,H,[4] N ( ‘oH CHL, - CgH,- SO,Na No.| Commercial Name. Scientific Name. Empirical Formula. 312 Acid Violet Sodium salt of C,,H,,N,0,5Na 4 BN. [B] hbenzyl-penta-methyl- HO 2 : . tri-amido-triphenyl- Acid Violet carbinol sulphonic 6 B. [By.] acid. 313; Alpine Blue. Sodium salt of CyoH,,N,0,)S,Na, (G] tetramethylethy1- z ; benzyl-triamido- ~ triphenylearbinol- HOw trisulphonic acid. 314 Acid Violet Sodium salt of Cy5H,,N,0,S,Na, 6 B. [A.] dimethyldibenzyl- HO—G pa aes triamido-triphenyl- carbinol-disulphonic acid. 315| Formyl Violet Sodium salt of C,,H,,N,0,8,Na, S4B. [C] tetraethyldibenzyl- HOZzeo Acid ‘Violet triamido-tripheny]- C2 ¥ 1026 carbinol-disulphonic 6 B. [G.] acid, 316 Red Violet eee at of Chiefly + ethylrosaniline- SMS he sulphonic acid. CagHooN so%sNag 317| Regina Purple. Acetate of mono- Acetate of o-tolyl- [B.S.S.] Regina Violet. Violet impérial rouge. Violet phenylique. phenyl or mono-o- tolyl-rosaniline mixed with the corre- sponding derivatives of pararosaniline, pararosaniline : CogHy,N 0. Acetate of o- 2)SO,N [1] CH fa] N(CH,), 2| SO, N [1 Cota Fy N(CH), [1] C,H, [4] N(C,H,)CH, - C,H,-S0,Na [1] C,H,[4] N (CH,), [1] C,H,[4] N (C,H,) CH, [1] C,H,[4] N (C,H;) CH, - CH, - $0,Na - gH, - $0,Na [1] C,H,[4] N (C,H,) CH, - C,H, -S0,Na <——[1] C,H,[4] N (C,H;), [1] CoH,[4] N (C,H,) CH, finer, [1] O,H,J [3] CH Lene caf tolyl-pararosaniline : H,-SO,Na some trisulphonic | acid. 324} Diphenylamine Sodium salt of Cy-H,,N,0,5,Naz [1] C,H,[4] NH - C,H, -SO,Na Blue. a C [1] C,H,[4] NH - C,H, -SO,Na "4 08a. . Bavarian Blue | elton | SD GGEIAIN CH “80a Soluble Blue 8 B and 10 B. [B.S.8.] 325; Methyl Blue. Sodium salt of Cy,HogN,8,0,Na, [1] C,H,[4] NH -C,H,-SO,Na [C] Ee C [1] C,H,[4] NH - C,H, -SO,Na Methyl Blue pararosanline- M BI for cotton. [0.] Brilliant Cotton Blue, greenish. [ By. ] XL Soluble Blue. [B.S.8.] Methyl Water Blue. [B.] trisulphonic acid. | [1] CjH,[4] N - C,H, -SO,Na ety yaaa Year of ) Behaviour with Reagents. Shade and Dyeing Properties. Discovery. Method of Employment. Discoverer. Patents. Method of Preparation. Literature. Action of sulphuric acid upon regina-violet spirit-soluble. Action of aniline on rosolic acid. (a) Action of oxalic acid upon diphenylamine. (6) Action of carbon hexa- chloride upon a mixture of diphenylamine and ditolyl- amine (obsolete), Action of cone. sulphuric acid upon diphenylamine-blue opal. Action of conc. sulphuric acid upon diphenylamine-blue opal. Action of cone. sulphuric acid upon diphenylamine-blue opal. Sulphonation of triphenyl-p- rosaniline formed by heating pararosaniline with aniline in presence of benzoic acid. Appearance of dyestuff: bronzy lumps or powder.—In water: violet solution.—On addition of hydrochloric acid to the aque- ous solution: separation of the sulphonic acid.—On addition of caustic soda to the aqueous solution: solution becomes a paler colour, but not colourless.—Dyes: wool reddish violet from an acid bath. 1862. J. PERSOz. GUINON MARNAS ET BONNET. Fr. Pat. of July 1862. BARRESWIL. Rep. Chim. Appl. 1862, p. 450. Appearance of dyestuff: dark blue powder with copper glance.— In water : insoluble.—In alcohol : blue solution.—On addition of hydrochloric acid to the alcoholic solution: no change.—On addition of caustic soda to the alcoholic solution: colour becomes yellowish red.—In conc. sulphuric acid: brownish yellow solution ; blue precipitate on dilution with water. 1866. Grrarp & Dr Larre. Traité des dérivés de la houille, p. 591. Eng. Pats. 1093 and 2686. Fr. Pat. of 21st May 1866. A. HAUSDORFER. Ber. (1890) 23, 1962. Appearance of dyestuff: brown powder.—In water: insoluble.— In alcohol: sparingly in the cold, more easily hot.—-In cone. sulphuric acid: brownish yellow solution; blue precipitate on dilution with water. Appearance of dyestuff: dark blue powder.—In water: insoluble cold, easily soluble on boiling with a blue colour.—On addition of hydrochloric acid to the aqueous solution : blue precipitate.— On addition of caustic soda to the aqueous solution: colour becomes grayish violet, on warming reddish brown.—In conc. sulphuric acid: reddish brown solution; blue precipitate on dilution with water.—Dyes : like alkali-blue (No. 327). Appearance of dyestuff: indigo blue powder.—In water: easily soluble with blue colour.—On addition of hydrochloric acid to the aqueous solution: colour becomes more intense.—On addi- tion of caustic soda to the aqueous solution: colour becomes brownish red.—In conc. sulphuric acid: yellowish brown solu- tion; blue on dilution with water.—Dyes: silk blue from a ‘* killed” soap bath. KALLE. Zeits. f. chem. Grossgew. 1, 189. Appearance of dyestuff: blue dull powder.—In water: blue solu- tion.—In alcohol: insoluble.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda to the aqueous solution: colour becomes brownish red.— In cone. sulphuric acid : yellowish brown solution, becoming green and then blue on dilution with water.—Dyes: silk and mordanted cotton blue. 1866. GIRARD & Dr LAIRE. Appearance of dyestuff: dark blue powder.—In water : blue solu- tion.—On addition of hydrochloric acid to the aqueous solution : no change.—On addition of caustic soda to the aqueous solu- tion : colour becomes reddish brown.—In conc. sulphuric acid : reddish brown solution; blue on dilution with water.—Dyes: mordanted cotton blue. 1862. E. C. NicHOLsoN. Eng. Pat. of 24th June 1862. [ 148 Constitutional Formula, No.| Commercial Name.: Scientific Name. Empirical Formula. 326; Aniline Blue, se aes pete : Hydrochloride - Hydrochloride : eee sulphate, or acetate ‘ ay Rake ao of triphenylrosaniline Cop Hay gC} fe [1] C,H,[4] NH.- C,H, od S81) [0] and lel CygHsN Cl oc) C,H,[4] NH - C,H, H.8.] LO. pararosaniline. i tT. Gos: Ho Spirit Blue. [B.S.5.] Sulphate : | um aa Cote ae [B.] [By.] [L.] C,,He)N,SO, and se Bite cas e. ie coe ? ae 2 P Gz. N.O, and [1] 6 aL4] Deen Bac Hessian Blue. [Z. ] go. 9e-\p 2 [1] C,H,[4] N - C,H, - HCl Bleu lumiére. CypHy,N 30. | | Bleu-de-nuit. 327} Alkali Blue.* peo ee a apne CygHegNgO,5 NB Rosaniline derivative - [B.S.S.] [4.] [B.] | Salts of triphenyl- and ([3] CH, rosaniline-monosul- 1G, 3 [By.] [0-] [Z.] [a2] phonic acid and tri- C,H,.N,0,5Na : [110 5\ [4] NH - C,H, -SO,Na Nicholson Blue. phenylpararosaniline- C [1] C,H,[4] NH - C,H, [B.S.S.] monosulphonic acid. | [1] C,H,[4] N - C,H, Fast Blue. [B.S.S.] 328| Soluble Blue.t Sys Segue Free acid : Rosaniline derwative, free acid : [B.8.8.] Fe ee a eee eer NEOs f{3]CH trisulphoniec acid 38° 313-9 1]C,H 8 Water Blue. (arith aon disul- and [CoH \[4] NH - C,H, -SO,H [B.] [By.] phonic acid) of tri- C..H.N.OS C<—[1]C,H,[4] NH - C,H, -SO,H Water Blue 6 B | phenylrosaniline and 37° 29°" 39 11C.H.[41N-C.H,-S0.H [ A,] triphenyl | [ ] & al ] ae : extra. | A. Lar China Blue. pararosaniline. [B.S.S.] [A.] [By.] London Blue extra. [B.S.S.] Cotton Blue. [L.] Opal Blue. [C.] Bleu Marine. 329| Alkali Blue X G. Sodium salts of sulphonic acids o [B.S.8.] Iph ek at of Soluble BlueXG.| ° amr [B.S.S.] ; Non-mordant Cotton Blue. [B.8.8.] 380| Methyldiphenyl- | Hydrochloride of CygH,4N3Cl [1] O.H, - N(CH,)C.H, amine Blue. readin heb igs 6) [1] C,H, - N(CH,)C,H pararosaniline. Go a oe 6 [M.] [1]C,H,-N-C,H, - HCl (No longer in com- merce. ) * The earliest blues, obtained without employment of acetic or benzoic acid and consequently incompletely phenylated and of red shade, came into dependent upon the degree of phenylation and is indicated by the suffix 3 R, 6 B, etc. + Vide note above. The name ‘Soluble Blue” was originally applied to the Alkali Blues, but was subsequently transferred to the — fio] Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: the hydrochloride forms a bronzy powder, the sulphate or acetate a bluish violet powder.—In water : insol- uble.—In alcohol: the acetate is easily soluble, the hydrochloride and sulphate much less readily.—On addition of hydrochloric acid to the alcoholic solution: no change.—On addition of caustic soda to the alcoholic solution : colour becomes brown- ish red.—In conc. sulphuric acid: brownish yellow solution ; blue precipitate on dilution with water.—Dyes: silk and wool greenish blue. Appearance of dyestuff.—light or dark blue powder.—In water : sparingly soluble cold, easily hot with a blue colour.—In alcohol : somewhat soluble.—On addition of hydrochloric acid to the aqueous solution : blue precipitate.—On addition of caustic soda to the aqueous solution: colour becomes reddish brown.—In conc. sulphuric acid: brownish red solution; blue on dilution with water.—Dyes : wool from a boiling bath made alkaline with borax, the colour being subsequently developed by passing through weak acid. : ; A Year of Discoverer. Patents. : Method of Preparation. Discovery. Literature. : Action of aniline, in presence 1860. Girard & Dr Larre. of acetic or benzoic acid, upon Fr. Pats. of 6th July 1860 rosaniline (containing some and 2nd January 1861. pararosaniline), Ding. Pol. J. 162, 297 ; 170, 58. | 1862. E. C. NIcHonson. Kng. Pat. of 24th June 1862. A. W. HormMann. Ann, (1864) 132, 160. Action of cone. sulphuric acid 1862. E. C. NicHo.son. upon opal blue (No. 326). Eng. Pat. 1857 of Ist June 1862. GILBEE. Eng. Pat. of 3rd July 1862. C. BuLK. Ber. (1872) 5, 417. Action of cone. sulphuric acid 1862. EK. C. NicHoLson. upon opal blue (No. 326). Eng. Pat. 1857 of 1st June 1862. Simpson, Mavunz, & NICHOLSON. C. BULK. Ber. (1872) 5, 419. Action of cone. sulphuric acid 1883. R. MELDoLA. upon the B-naphthylated Chem. News, 28rd & 30th March rosaniline obtained by heating eho ee: Fl hie rosaniline with B-naphthyl- ROOKE, SIMPSON, & SPILLER. amine. Action of oxalic acid, copper 1874. Cu. GIRARD. nitrate or chloranil upon methyldiphenylamine. higher sulphonic acids. (with oxalic acid.) Eng. Pat. 2347 of 4th July 1874. Ber. (1876) 9, 641. Barpy and Dusart. (with cupric nitrate.) J. R. Guiey. MaistEr, Lucius, & BRUNING, (with chloranil.) Ger. Pat. 8251 (expired). Appearance of dyestuff: blue glistening powder, or coppery flakes. —In water: blue solution.—In alcohol: nearly insoluble.—On addition of hydrochloric acid to the aqueous solution: colour not altered, more or less precipitate of disulphonie acid.—On addition of caustic soda to the aqueous solution: colour becomes brownish red.—In conc. sulphuric acid: dark reddish yellow solution; blue solution and precipitate on dilution with water.—Dyes : silk and mordanted cotton blue, Alkali blue X G: Appearance of dyestuff: grayish black lumps.—In water: greenish blue solution.—On addition of hydrochloric acid: blue precipi- tate.—On addition of caustic soda: violet black solution and precipitate, on heating the precipitate gums together leaving a colourless solution.—In cone. sulphuric acid: reddish brown solution; blue precipitate on dilution.—After reduction with zinc dust: colour does not return on paper.—Dyes: like an ordinary alkali blue but is greener in shade. Soluble blue X G: Appearance of dyestuff: flakes with reddish metallic lustre.—In water: blue solution.—On addition of hydrochloric acid : com- plete precipitation, blue precipitate. —On addition of caustic soda : dull claret colour.—In conc. sulphuric acid : reddish brown solution ; blue precipitate on dilution with water.—After reduc- tion with zine dust: colour does not return on paper.—Dyes: cotton and silk from an acid bath. Appearance of dyestuff (prepared with chloranil): coppery lumps smelling of chloranil.—In water: insoluble; on heating a smell of methyldiphenylamine becomes apparent.—In alcohol: blue solution.—On addition of hydrochloric acid to the alcoholic solution : no change.—On addition of caustic soda tc the alco- holic solution: colour becomes red.—In conc. sulphuric acid : brownish yellow solution ; blue precipitate on dilution with water. commerce as Bleu do Paris and Bleude Lyon. The shade of the various brands of rosaniline blues (spirit blues, alkali blues, and soluble blues) is chiefly The hydrochloride of tri-p-tolyl-rosaniline comes into commerce as Greenish Blue [.]. Lower qualities of Alkali Blue appear in commerce as Guernsey Blue, of soluble-blue as Serge Blue, etc. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 331) Alkali Violet. Sodium a of C,,H,)N,0,5Na [1] C,H,[4] N(C,H;), > tetraethyl- ed monomethylphenyl- HO-C [1] C,H{4] NOt pararosaniline- monosulphonic acid. [1] CoH,{4] N—=GaHi Or 2|0[2 0:[4]¢, Hae a ie ONa C,H, -CO,Na 343 Chrysoline. Sodium salt of C.H, ,0,Nas 2 O Pao benzy1-fluoresceine. A es NaO- CoHs< > CoH (ONa) CH, - CoH; OC——O,H, 4 344 Aureosine. A chlorinated (No longer in com- fluoresceine. merce. ) 345 Rubeosine. A nitrochloro- (No longer in com- fluoresceine. merce. ) * At one time methylfluoresceine also ileal y | as ear of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Method of Preparation. Discovery. Literature. Method of Employment. u Oxidation of the methyl ethers 1835. {EICHENBACH. Appearance of dyestuff: crystalline powder, melts with decomposi- of pyrogallol and methyl- Berz. Jahresber. (1835) 14, 385. tion at 200°.—In alkalies : blue solution.—On addition of caustic pyrogallol. 1876. GRATZEL. : soda to the aqueous solution of the alkaline salts: blue floc- ee e i sae ae ae culent precipitate.—Dyes: wool and silk orange in acid solution, 8 nee (1878) iL, can : in ammoniacal solution more especially upon a tin mordant, bluish LIEBERMANN. oleh. Ber. (1876) 9, 334; (1878) 11, 1104. A. W. HoFFMANN. Ber. 11, 1455; 12, 1871, 2261. Action of formaldehyde, or 1889. Tr. SANDMEYER. Appearance of dyestuff : chocolate powder.—In water: dark red methyl alcohol and sodium J. R. Guicy & Co. solution.—On addition of hydrochloric acid to the aqueous solu- nitrite, upon a solution of Eng. Pat. 333389. tion : the free acid is precipitated.—On addition of caustic soda salicylic acid in conc. sulphuric Am. Pat. 410739. to the aqueous solution : light brown solution.—In cone, sul- acid. Ger. Pat. 499708. phuric acid: brown solution; separation of the colour acid on Chem. Ztg. (1889) 22 267 ; (1890) dilution with water.—Employment : for calico printing. Re Centralbl. f. eee 1889, 982. J. Soc. Dyers and Colorists, 1889, 170. Heating phenol with phthalic 1871. Ap. BAEYER. ‘| Appearance of dyestuff: brownish yellow crystals.—In water : in- anhydride and a dehydrating Ber. (1871) 4, 658 ; (1876) 9, 1230. soluble.—In aqueous caustic soda: easily soluble with magenta agent. Ann. (1880) 202, 68. red colour.—On addition of hydrochloric acid to the alkaline solution: separation of phenol phthalein.—In conc. sulphuric acid: yellowish brown solution; precipitated on dilution with water.—Employment : as an indicator in alkalimetry. Action of nitric acid upon 1889, CO. Dreyrus, H. Burt & | Appearance of dyestuff: orange yellow powder.—In water: deep phenol-phthaleine dissolved in J. HALL. yellow solution.—In alcohol: deep yellow solution.—On addition sulphuric acid. THE CLAYTON ANILINE Co., of hydrochloric acid to the aqueous solution : tetranitrophenol- LIMITED. phthaleine (m. p. 244°) separates out.—On addition of caustic soda Eng. Pat. 344199. to the aqueous solution : no change.—Dyes: wool orange yellow Ger. Pat. 5221189. from a bath acidified with acetic acid, or upon a chromium or The Dyer (1890) 10, 70. alumina mordant. J. Soc. Chem. Ind. (1890) 9, 285. J. Soc. Dyers and Colorists, 1890, 32. Heating resorcinol with phthalic! 1871. Ap. BAEYER. Appearance of dyestuff: yellowish brown powder.—In water: anhydride, alone or in presence Ber. (1871) 4, 558, 662; (1875) 8, 146. yellow solution, with intense green fluorescence visible in extreme of zinc chloride or sulphuric Ann. (1876) 183, 2; (1882) 212, 347. dilution.—In alcohol: easily soluble.—On addition of hydro- werd: K. FISCHER. chloric acid to the aqueous solution: yellow precipitate.—On Ber. (1874) 7, 1211. addition of caustic soda to the aqueous solution : the colour and Spee een oO fluorescence become darker.—In conc. sulphuric acid: yellow 675. solution with very slight fluorescence; yellow solution on dilution Ding. Pol. J. (1887) 263, 49 ; (1892) with water.—Dyes : silk and wool yellow. 283, 182 R. Mnver & O. Oppetr. Ber. 21, 3376. A. BERNTHSEN. Chem. Zeit. (1892) 16, 1956. J. Soc. Chem. Ind. 1893, 513. Heating resorcinol with phthalic 1877. F. REvVERDIN. Appearance of dyestuff : reddish brown powder or lumps, smelling anhydride and benzyl chloride Mon. Scien. (1877) 860. of benzyl chloride.—In water: brown solution with green fluores- a presence of sulphuric acid. Zeits. f. Chem. Grossgewerbe cence.—On addition of hydrochloric acid to the aqueous solu. (1877) 2, 456, 668 ; (1878) 3, 625. tion: brownish yellow precipitate.—On addition of caustic soda DDE LS to the aqueous solution: colour becomes darker.—In cone. sulphuric acid: yellow solution; yellow precipitate on dilution with water.—Dyes: silk yellow. Action of hypochlorous acid on| 1876. | Ep. Wiim, G. Boucnarpat| Appearance of dyestuff: (as free acid) yellowish red powder and fluoresceine. & Gr GIRARD. lumps.—In water : scarcely soluble.—In aqueous sodium carbon- Ger. Pat. 2618 (expired). ate: easily soluble with yellowish brown colour and green fluor- escence.—In cone. sulphuric acid : yellow solution ; orange yellow precipitate on dilution. Action of nitric acid upon 1876. Ep. Wiuim, G. BoucHarpatT| Appearance of dyestuff: (as free acid) brownish yellow powder.— aureosine. came into commerce under this name. In water : insoluble.—In alcohol: brownish yellow solution with green fluorescence.—In aqueous caustic soda: red solution with green fluorescence.—In conc. sulphuric acid: yellow solution ; yellow precipitate on dilution with water. & Cu. GIRARD. Ger. Pat. 2618 (expired). [ 154 ] No.} Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 346 Fosine.* [B. Alkali salts of tetra- C,,H,O,.Br,Na,, 21012 Eosine, shat bromo-fluoresceine. eat NaO [4] C,HBr, i C HCH Bn A] ONa [A.] [B.S.8.] Eosine A. [B.] Eosine G G F. [0.] OC Cae Water-soluble on / Eosine. [1/.] 21019 Fosine B. 0:[4] CpHB ry <4 : Lt > CHB [4] ONa Eosine A extra. [D.H.] oe Eosine 3 J and Oe 4 J extra. [L.] 347 Erythrine. Potassium salt of C,,H,Br,0,K 210f2 Spirit Eosine. tetrabromo- at ret 0 :[4] ChHB p<} 6 b> CoH Bal] OK [B.] RS eee 1er. Primerose & Ho C,H, - CO,CH, Valcool. [D.H.] Methyl Eosine. [Mo. | [Z.] 348] Spirit Eosine. Potassium salt of CoH Br. On ke 210 f2 7 Ethyl Eosine. tetrabromo- Babi eae O :[4] CHB CyB 4] OK Eosine §. [B.] he Nance PF Eosine B B. [J.] C,H, -CO,C,H, Primerose a Yalcool. Eosine a lalcool. Rose J Ba l’alcool. 349| Hosine BN. [B.] | Potassium or sodium | C,,.H,N,O,Br,K, |,- 210 f2 Aca Fs aalt of dibrome- BO ORS By EO |e (NO, <4 C by CoB (NO,) [4] OK [L.] [BS 8] dinitro-fluoresceine. Methyl Eosine [4.] OG _C Eosine B W. Or Scarlet J, JJ, and 21012 V. [Mo] 0: [4] CHBr(NO,)< a tp Coe (NO,) [4] 0K Eosine Scarlet B. [C.] C,H, - 00,K Fosine B. [L.] 3 i Sodi tassi % 5 6 50 Erythrosine. odium or potassium CooHOstah ay NaO [4] C,H, gl O hae CHI,[4] ONa [B.] (M.] [B.S.S.] Erythrosine D. [0] Erythrosine B. [4] Pyrosine B. [Mo.] Todeosine B. Eosine, bluish. Eosine J. [B.] Dianthine B. Rose B a leau. [1] Primerose soluble. [D. H.] salt of tetraiodo- fluoresceine. [1] C[1] OC-—C,H, Or 0: [4] CHL Coll, [4] ONa C,H, -CO,Na * Varying mixtures of di- and tetra-bromo-fluoresceine come into Year of Method of Preparation. Discovery, Discoverer. Patents. Literature. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Bromination of fluoresceine in 1874. aqueous or alcoholic solution. Methylation of Eosine. 1874. Ethylation of Eosine. 1874. (a) Nitration of dibromofluor- 1875. esceine in aqueous solution. (6) Bromination of dinitro- fluoresceine in alcoholic solution.) 1876. Todation of fluoresceine in 1876. aqueous or alcoholic solution. H. Caro. Bap. ANIL. & SopA FABRIK. A. W. HorMann. Ber. (1875) 8, 62. AD. BAEYER. Ber. (1875) 8, 147. Ann. (1876) 183, 2. O. MUHLHAUSER. Ding. Pol. J. (1887) 263, 49 ; (1892) 284, 21 and 46, J. Chem. Ind. 1887, 283 ; 1892, 673. A. BERNTHSEN. Chem. Zeit. (1892) 16, 1956. J. Soc. Chem. Ind. 1898, 513. H. Caro. Bap, ANIL. & SopA FABRIK. Ap. BABYER. Ann. (1876) 183, 53. A. BERNTHSEN. Chem. Zeit. (1892) 16, 1956. J. Soc. Chem. Ind. 1893, 513. Appearance of dyestuff: small bluish red glistening crystals or brownish red powder.—In water : bluish red solution ; the dilute solution has a green fluorescence.—In alcohol : easily soluble with bluish red colour and yellowish green fluorescence.—On addition of hydrochloric acid to the aqueous solution: yellowish red precipitate.-— On addition of caustic soda to the aqueous solu- tion: no change.—In conc. sulphuric acid: yellow solution; yellowish red precipitate on dilution with water.—Dyes : wool and silk yellowish red.—Largely employed for making pigments (“vermilionette,” etc.), for which purpose it is usually precipitated as an insoluble lead lake, upon a basis of red-lead, orange-lead, white-lead, ete. Appearance of dyestuff: green glistening powder or flakes.—In water: sparingly soluble cold, more readily on boiling, with a cherry red colour.—In alcohol: red solution with brownish yellow fluorescence.—On addition of hydrochloric acid to the aqueous solution : brownish yellow precipitate.—On addition of caustic soda to the aqueous solution: the colour and fluorescence becomes darker.—In conc. sulphuric acid: yellow solutiqn ; evolves bromine on heating.—Dyes: silk bluish red with reddish fluorescence. H. Caro. Bap. Antn. & Sopa FABRIK. Ap. BAEYER. Ann. (1876) 183, 46. O. MUHLHAUSER. Ding. Pol. J. (1887) 263, 49 and 99 ; (1892) 283, 210. J. Chem. Ind. 1887, 283 ; 1892, 675. H. Caro. Bap. ANrIL. & SoDA FABRIK. Ap. BARYER. Ann. (1876) 183, 61. O. MUHLHAUSER. Ding. Pol. J. 263, 49, 99. J. Soc. Chem, Ind. 1887, 283; 1892, 739. BINDSCHEDLER & BUSCH. O. MUHLHAUSER. Ding. Pol. J. 263, 49, 99 ; 283, 258, J. Chem. Ind. (1887), 283 ; (1892), 677. commerce as Eosine-Orange [/.], Eosine 3 G. [C.], Salmon Pink, etc. Appearance of dyestuff: brown powder mixed with small green crystals.—In water : sparingly soluble cold, soluble on boiling to a cherry red solution with slight greenish yellow fluorescence.— On addition of hydrochloric acid to the aqueous solution : yellowish brown precipitate.—On addition of caustic soda to the aqueous solution: brownish yellow precipitate.—In conc. sul- phuric acid: yellow solution ; on warming bromine is evolved,— Dyes: wool yellowish red with slight fluorescence. Appearance of dyestuff: brown crystalline powder.—In water: yellowish red solution.—On addition of hydrochloric acid to the aqueous solution: yellowish green floceulent precipitate.—On addition of caustic soda to the aqueous solution : no change.— In conc, sulphuric acid: brownish yellow solution, evolves bromine on heating ; brownish yellow precipitate on dilution with water.—Dyes : silk and wool bluish red. Appearance of dyestuff: brown powder.—In water: cherry red solution without fluorescence.—On addition of hydrochloric acid to the aqueous solution : brownish yellow precipitate.—On addi- tion of caustic soda to the aqueous solution : no change.—In conc. sulphuric acid: brownish yellow solution ; evolves iodine vapours on heating; brownish yellow precipitate on dilution with water.—Dyes: silk and wool bluish red. [ 156 No. |. Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 351| Erythrosine G. Sodium or C..H.0-1,Na, 2 ‘ f [B.] potassium salt of nose ores NaO [4] OHI CoHB rl] OK Phioxine fluoresceine. New Pink. OC—C,H,Cl, Or OW? 0: [4] ChHBr, CoHBrs[4] OK C,H,Cl, - CO,K Cyanosine. Alkaline salt of Co, HCl. BrO-K d 2]0[2 au Mi tetrabromodichloro- | © sig A Se O:[4] CyB tH} Ca b> Co HBry[ 4] OK fluoresceine- methyl-ether. C,H,Cl, - CO,CH, 354 Rose Bengal. Alkaline salt of Ce, Cl, OK 910 (2 [B ] - tetraiododichloro- a aS Sa KO [4] CHIa Coal] OK Rose Bengal N fluoresceine. ) [C.] e x OC——C,H,Cl, Or } DO 0:[4] CHIH} : t > Col 4) OK C,H,Cl, -CO,K | ' 365! Phloxine. Sodium salt of | OC, H,Cl,Br,0,Na 2]0[2 ‘ [a] tetrabromotetra- EE ODE OM: NaO [4] CpHB <3} OH p> CoHBrL 4] ONa Phipens TA chlorofluoresceine. [ Mo. ] Erythrosine B. OC—C,Cl, [/.] Or DANO 0 :[4] ChB CHB 4] ONa C,Cl, -CO,Na 3 Cvanosine B. Sodium salt of Ol 2|0[2 sear Sodium salt of | O,9H,C1,Br,0,Na | 9.74) CHB CyB 4] ONa ; chlorofluoresceine- ethy!-ether. C,Cl, - CO,C,H, * A mixture of the alkaline salts of diiodo- and tetraiodo-fluorescein e Method of Preparation. Iodation of fluoresceine in _ aqueous solution. Action of bromine on dichloro- fluoresceine from dichloro- phthalic acid and resorcinol. Methylation of phloxine. Action of iodine upon dichloro- fluoresceine obtained from dichlorophthalic acid and resorcinol. Bromination of tetrachloro- fluoresceine obtained from tetrachlorophthalic acid and resorcinol. Ethylation of tetrabromotetra- chloro-fluoresceine. Year of Discovery. 1875. 1875. 1876. 1875. 1882. 1882. [ 157 Discoverer. Patents. Literature. E. N6.LTING. E. N6LTING. JOHN CASTELHAZ. Eng. Pat. 4477. E. NOLTING. E. NOLTING. R. GNEHM. R. GNEHM. comes into commerce as Pyrosine R [M.], or Ponceau d’Orient. ] Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: yellowish brown powder.—In water: cherry red solution without fluorescence.—On addition of hydro- chloric acid to the aqueous solution: brownish yellow precipi- tate.—On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: brownish yellow solution; evolves iodine vapours on heating; brownish yellow precipitate on dilution with water.—Dyes: wool yellowish red with yellowish red fluorescence. Appearance of dyestuff: brownish yellow powder.—In water: cherry red solution with greenish yellow fluorescence.—On addi- tion of hydrochloric acid to the aqueous solution: brownish yellow precipitate on warming.—On addition of caustic soda to the aqueous solution: colour becomes a bluer red.—In conc. sulphuric acid: brownish yellow solution, no change on heating ; brown precipitate on dilution with water.—Dyes: wool bluish red without fluorescence. Appearance of dyestuff: brownish red powder.—In water: in- soluble cold, slightly on boiling.—In alcohol: bluish red solution with reddish yellow fluorescence.—On addition of hydrochloric acid to the alcoholic solution: the fluorescence disappears.—On addition of caustic soda to the alcoholic solution : no change. —In conc. sulphuric acid: yellow solution; evolves bromine on heating ; reddish brown precipitate on dilution with water. Appearance of dyestuff: brown powder.—In water: cherry red solution without fluorescence.—On addition of hydrochloric acid to the aqueous solution : brownish red precipitate.—On addition of caustic soda to the aqueous solution; no change. —In conc. sulphuric acid : brownish yellow solution, evolves iodine vapours on heating; brownish red flocculent precipitate on dilution with water.—Dyes : wool bluish red without fluorescence. Appearance of dyestuff: brick red powder.—In water: easily soluble with bluish red colour and slight dark green fluorescence. —In alcohol: bluish red solution with brick red fluorescence.— On addivion of hydrochloric acid to the aqueous solution : de- colourised with separation of a reddish precipitate.—On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: yellow solution; yellowish red precipitate on dilution with water. Appearance of dyestuff: red crystalline powder.—In water: sparingly soluble with red colour and yellow fluorescence.—On addition of hydrochloric acid to the aqueous solution : brownish red flocculent precipitate.—On addition of caustic soda: colour becomes rather darker.—In conc. sulphuric acid: yellowish brown solution ; brownish red precipitate on dilution with water. —Dyes: wool bluish red. Constitutional Formula. Pee No.} Commercial Name. Scientifie Name. Empirical Formula. 357| Rose Bengal B. Potassium salt of Cap ll,Cl,LO.Ks [L.] tetraiodotetra- et ‘ Rete Bera chlorofluoresceine. [ B.] [C.] 358 : : Hydrochloride of C,.H., N,O.C1 Sr aaa & diethyl-m-amido- 2 le a8 : ; phenol-phthaleine. 359| Rhodamine S. Hydrochloride of Coton NeUnGL [By] dimethyl-m-amido- Ne ee Be , phenol-succineine. 360| Rhodamine S. Hydrochloride of C,,H,,N,0,Cl diethyl-m-amido- phenol-succineine. [B.] [By] (C,H,),N [4] C,H, <1! 2 Pon, [4]NC,H,),HCl Cl (CjH;),N : [4] C,H CoA] OK C,Cl, -CO,K [1] [1] @C—,H, Or »Sfaje fa] C,H, - CO,H [1] 0 [1] OC——C,H, Or C1(CH,),N : [4] CH CHL] N(C,H,,| C,H, - CO,H fio Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: brownish red powder.—In water: bluish red solution without fluorescence.—On addition of hydrochloric acid to the aqueous solution : flesh pink flocculent precipitate. —On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid: brown solution; flesh pink precipitate on dilution with water,—Dyes: wool bluish red. ee ee ee, ee es a Appearance of dyestuff: green crystals or reddish violet powder.— In water or alcohol: easily soluble with bluish red colour, and strong fuorescence in dilute solution ; fluorescence of the alcoholic solution disappears on heating and returns again on cooling.—On addition of hydrochloric acid to the aqueous solu- tion: separation of green crystals of the hydrochloride, which dissolve in excess to a scarlet red solution which is turned bluer on dilution with water.—On addition of caustic soda to the aqueous solution: small quantity in the cold produces little change, larger quantity or heating the solution throws down a rose red precipitate, soluble in ether or benzene to a colourless solution.—On heating with strong aqueous caustic soda: smell of dimethylamine.—In conc. sulphuric acid: yellowish brown solution with evolution of hydrochloric acid ; becomes scarlet red and finally bluish red on dilution with water.—Dyes: wool and silk fast shades of bluish red with strong fluorescence, tannined cotton violet red without fluorescence, oiled cotton with fluores- Appearance of dyestuff: dark crystalline powder.—_In water : easily soluble with red colour and yellow fluorescence.—On addition of caustic soda to the aqueous solution : slowly decolourised.—In cone. sulphuric acid : yellow solution without fluorescence ; rose red solution on dilution with water.—Dyes : red upon unmordanted cotton or cotton mordanted with tannin and tartar emetic.— Employment: for dyeing half silk materials, and for colouring : Year of Discoverer. Patents. Method of Preparation. Discovery. Literature. Action of iodine upon tetra- 1882. Rh. GNEHM. chlorofluoresceine obtained from tetrachlorophthalic acid and resorcinol, (a) Heating phthalic anhydride} 1887. M. CERESOLE. with diethyl-m-amidophenol. Bap. Anin. & SoDA (b) Action of diethylamine upon FABRIK. fluoresceine-chloride. King. Pat. 15374", Am. Pats. 377349 & 37735088, Ger. Pat. 4400287, Fr. Pat. 186697°. Meister, Lucrus, and i BrUNING. Eng. Pat. 960088. Ger. Pat. 4836758. A. BERNTHSEN. Chem. Zeit. (1892) 16, 1956. J. Soc. Chem. Ind, 1893, 513. cence. x Heating succinic anhydride} 1888. M. Kaun. with dimethyl-m-amido-phenol. MAsERt. (b) Heating resorcinol-succin- R. GNEHM, eine with dimethylamine at Am. Pat. 425504. 170°-200°. Fr. BAYER & Co. Ger. Pat. 5198358, assigned to the Bap. Antu. & SopA paper-pulp and wood, FABRIK. Farberztg. (1890) 26, 267. Soc. CHmM. INDUSTRIE IN BASEL. Eng. Pat. 10047%. Heating succinic anhydride 1887. M. CERESOLE. with diethyl-m-amido-phenol. SS ee ee ee R. GNEHM. Am. Pat. 402436. Bap. ANIL. & SopAa FABRIK. Fr. Bayer & Co. Eng. Pat. 2635°%. Ger. Pat. 5198388. Fr. Pat. 194908. Appearance of dyestuff: green crystals or brown powder.—In water : easily soluble with red colour and strong fluorescence.— On addition of a little hydrochloric acid to the aqueous solu- tion : slow precipitation, the precipitate being soluble in excess of hydrochloric acid to a scarlet red solution, which becomes bluish red on dilution with water.—On addition of a little caustic soda to the aqueous solution: no change in the cold, becomes bluer on heating.—In conc. sulphuric acid: yellowish red solution.— Dyes: a yellower shade than rhodamine B, and has a greater affinity for cotton. [ 160 No.|} Commercial Name. 361 Cyclamine, [ Mo.] Scientific Name. Empirical Formula. 362 Galleine. [B.] [By.] [MJ Alizarine Violet. Anthracene Violet. 363 Coeruleine. [B.] [By.] [A] Alizarine Green. Anthracene Green. 364 Coeruleine S. [B.] [By.] IM] Alizarine Green. Anthracene Green. Oxidation product of pyrogallol- phthaleine. Sodium bisulphite compound of ceeruleine. CoH, 0, C,)H,0 CoH 99).S,Na, Constitutional Formula. | KO. CHI, <8 >C,HI,- OK | OC_C,6am | oe HO - C,H, <@>C,H, - OH OC O;Hy 26 C,H, <(>O,H (OH)-0 es 0—C , H,—_ 0 C C,H, <;>C,H (OH)-0 ee 0—C ,H,——O +2 NaHSO, No.| Commercial Name. 365 Indophenol. [D.H.] 366 |Indophenol White. [D.H.] [C.] Leucindophenol. Scientific Name. Oxidation product of dimethyl-p-amido- phenyl-p-oxy-a- naphthylamine. Tin compound of dimethyl-p-amido- phenyl-p-oxy-a- naphthylamine. Empirical Formula. CygH,,N,0 CygHsN,0 Constitutional Formula. 1] C.H,[4] N (CH,) No ft OH 3] OH 3] [3] 370| Gallanilic Violet | Sodium-bisulphite Probably : Probably : BS. [D.H.] ete C,sH,N,0,C1 [1] anhydride-anilide. + NaHSO, Cl(CH,),N [4] Cpa >C,H(OH), - CO [2] | +NaHiso, — 37 372 Gallanilic Indigo PS. [D.H.] Meldola’s Blue. New Blue. [0-] [By] Naphthylene Blue R in crystals. [By.] Fast Blue 2 B for cotton. [ A.] Fast Blue R for cotton, in crystals. [.A.] Cotton Blue R. [B] Metamine Blue B&G. [L.] Chloride of dimethy]l- C,H,NH - OC - C,H,(OH),- 0 C,H, ,NOC1 [1] phenylammonium-f- i naphthoxazine. Cl(CH.),N [4] CoHs< 9 > Cros | [2] AND THIAZINES. Method of Preparation. Action of nitroso-dimethyl- aniline hydrochloride upon sym. dioxybenzoic acid. Action of nitroso-dimethyl- aniline hydrochloride upon gallic acid or tannin. Action of nitroso-dimethyl- aniline hydrochloride upon the methyl ether of gallic acid. Action of nitroso-dimethy]- aniline hydrochloride upon tannin-anilide, and treatment of the product with sodium hydric sulphite. Sulphonation of the product of the action of aniline (or toluidine, etc.) upon the con- | densation-product of nitrosodi- methylaniline hydrochloride with tannin-anilide. Action of nitroso-dimethyl- aniline hydrochloride upon B-naphthol. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Discovery. Literature. Method of Employment. 1890. R. Boun. Appearance of dyestuff: black paste.—In water: sparingly soluble Bap. ANtL. & SopA cold, more readily hot.—In alcohol: violet solution with strong FABRIK. red fluorescence.—On addition of hydrochloric acid to the Eng. Pat. 12356. paste: magenta red solution.—On addition of caustic soda to Am. Pat. 440536%. the paste: bluish violet solution—In conc. sulphuric acid: Ger. Pat. 57938%. indigo blue solution; magenta red on dilution with water.—Dyes : Fr. Pat. 2073932. a violet blue on chrome mordanted wool or cotton. 1881. H. K6cuHtin. Appearance of dyestuff: usually a greenish gray paste; when dry a Ger. Pat. 1958081. bronzy powder.—In water : insoluble.—In alcohol: bluish violet Eng. Pat. 489981, solution.—On addition of hydrochloric acid to the paste: pale Am. Pats. 253721 & 257498. magenta red solution.—On addition of caustic soda to the Mon. Scien. (1883) [3] 13, 292. paste : reddish violet solution.—In conc. sulphuric acid: corn- Bull. de Mulhouse (1883) 53, 206. flower blue solution; magenta red on dilution with water. — R. Nrerzki & R. Orro, Employment: dyes chrome mordanted wool bluish violet, and is , oe ou eT pelea _ | employed in printing upon chrome mordanted wool and cotton. 180g N 1S fe 1886, A. KERN. Appearance of dyestuff: brown glistening crystals, or dark brown Eng. Pat. 595387, powder.—In water: easily soluble.—In alcohol: bluish violet Am. Pat. 396574. solution.—On addition of hydrochloric acid to the aqueous Ger. Pat. 4578687. solution : colour becomes magenta red.—On addition of caustic R. Nrerzxr & R. Orro. soda to the aqueous solution : brown precipitate which dissolves Ber, 21, 1742; 25, 2994. in excess to a violet solution.—In conc. sulphuric acid : corn- flower blue solution ; magenta red on dilution with water.—Dyes : tannin mordanted cotton, or chrome mordanted wool or cotton, bluish violet. 1889. MouLER. Appearance of dyestuff: black fluid paste.—In*water or alcohol: L. Duranp, HucuEentn very sparingly soluble, with a blue colour.—On addition of and Co. caustic soda to the aqueous or alcoholic solution : bright bluish Rn ot 89 89 violet colour.—In conc. sulphuric acid: grayish red solution ; Fes sad eens 4 See s dull claret on dilution with water.—Dyes: metallic mordanted and 451 502. 4 wool or silk, shades of violet redder than gallocyanine ; direct from Nierzxi and Bosst. an acid bath bluer shades, Ber. 25, 2995. 1891. L. DurAnp, HucuENIN Appearance of dyestuff: bluish black powder or paste.—In water and Co. or alcohol: pure blue solution.—On addition of hydrochloric Ene. Pat. 5839, acid: dark blue precipitate, leaving the solution light reddish Ris. Pats 444538. brown.—In cone. sulphuric acid: cherry red solution.—Dyes: wool and silk blue from an acid bath, chromed wool bluish green. 1879 R. MELDOLA. Appearance of dyestuff: dark violet bronzy powder, or crystals; the Ber. (1879) 12, 2065. A. BERNTHSEN. Verh. Heidl. (1886) 3, 5, Heft. F. REVERDIN & E. NOLTING. Sur la constitution de la naphta- line et de ses dérivés, page 72. R. Nimrzxi and R. OTto. Ber. (1888) 21, 1745. O. N. Wirt. Ber. (1890) 28, 2247. R. Nrerzxi and A. Bossi. Ber. 25, 2994. powder is excessively irritating to the mucous membrane.—In water : easily soluble with bluish violet colour.—In alcohol: blue solution.—On addition of hydrochloric acid to the aqueous solution: the violet solution becomes blue.—On addition of caustic soda to the aqueous solution: brown precipitate.—In conc. sulphuric acid: blackish green solution; blue on dilution with water.—Dyes: cotton mordanted with tannin and tartar emetic indigo blue. No. 3/3 374 375 378 379 380 [ 164 Commercial Name. Scientific Name. New Methylene Blue G G. [C.] Muscarine. [D.H.] Nile Blue A. - [B.] [By-] Nile Blue 2 B. [B.] Chloride of dimethyl- phenylammonium-f- oxy-B-naphthoxazine. Sulphate of dimethyl- phenylammonium- a-amido-6- naphthoxazine. Sulphate of diethyl- phenylammonium- a-benzylamido-p- naphthoxazine. Capri Blue. [L.] Fast Black. [L.] Black Paste. Fast Blue Black. [Z.] Gallamine Blue. [G.] Chloride of dimethyl- tolylammonium- dimethyl-amido- phenoxazine. Fluorescent Blue. [1] Resorcin Blue. [K.S.] Bleu Fluorescent. [Z.] Ammonium salt of tetrabromoresorufin. Empirical Formula. Constitutional Formula. C,sH,,N,0,C1 Sulphate : (CysHygN,0),80, C,,H,,N,OC1 CygH,;NOCl, C,,H,Br,N,O, we aonss-CC Ok /\ [1] C1CH,),N [4] CoH

Croll [7] OH [2] Hydrochloride - a CUCH,)_N [4] C,H << >CyoHs [4] NHy | [2] Chloride - i CM(CyH,).N [4] CyHy<) > CoH, [4] NH-CyHy [2] MN CUCH,).N-C,Hy(CH.)CpHl, [4] N(CH) [2] C1C,H, Br 0 Br Oo— OH Br \N ‘Br Ls [r 165 : Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Method of Preparation. Discovery. Literature. Method of Employment. Action of dimethylaniline and 1890. M. HorrMANN and Appearance of dyestuff: greenish gray powder.—In water: blue oxidising agents upon dimethyl- A. WIENBERG. solution.—In alcohol : greenish blue solution.—On addition of phenylammonium-f-naphth- L. CAsSsELLA & Co. hydrochloric acid to the aqueous solution: no change, brown oxazine chloride (Meldola’s Ene. Pat. 6946. with excess.—On addition of caustic soda to the aqueous Blue). reloe SCHLARB. solution: bluish black precipitate.—In conc. sulphuric acid: Chem. Zeit. (1891) 15, 1281, 1387. reddish brown solution; dull green and finally pure blue on J. Soc. Chem. Ind. (1892) 25. dilution with water.—Dyes : cotton mordanted with tannin a very Soc. Dyers & Colorists 1893, 15. greenish blue. - | Action of nitroso-dimethyl- 1885. J. ANNAHEIM. Appearance of dyestuff: brown violet powder.—In water: sparingly aniline hydrochloride upon DurRAND & HvuQuENIN. soluble cold, easily hot, with a bluish violet colour.—On addition (2: 7)-dioxynaphthalene. Nierzki1 & Bosst. of hydrochloric acid to the aqueous solution: bluish violet | Ber. 25, 3002. precipitate.—On addition of caustic soda to the aqueous solu- tion: colour becomes yellowish brown.—After reduction with zinc dust: colour returns on exposure to air.—In conc. sulphuric acid: bluish green solution; on dilution with water the solution becomes blue, then violet, and finally gives a violet precipitate.— Dyes: cotton mordanted with tannin and tartar emetic blue. (a) Action of nitroso-dimethyl- 1888. Tx. REIssIc. Appearance of dyestuff (sulphate): bronzy crystalline powder.—In m-amidophenol hydrochloride BAp. Antu. & SopA water : sparingly soluble cold, easily hot with a blue colour.—In upon a-naphthylamine. FABRIK. ; alcohol: blue solution.—On addition of hydrochloric acid to (b) Action of a-naphthoquinone- Eng. Pats. 4476°8 & 11046. the warm aqueous solution : precipitates the hydrochloride in dichlorimide upon dimethyl- . Am. Pat. 431541, small needles, which appear violet by transmitted, green by m-amido-phenol in alcoholic Ger. Pat. 4526888. reflected light.—On addition of caustic soda to the aqueous solution. Fr. Pat. 18935988, solution : red precipitate, soluble in ether to a brownish orange Fr. BAYER & Co. solution with dark green fluorescence.—In conc. sulphuric acid : ; Ger. Pat. 4984499. yellow solution, green and then blue on dilution with water.— i 5 Dyes: cotton mordanted with tannin and tartar emetic blue. : Action of nitroso-diethyl- 1891. P. Juyivus. Appearance of dyestuff: green powder with metallic lustre.—In m-amido-phenol-hydrochloride Bap. Anru. & Sopa water : sparingly soluble cold, more readily hot to a blue solution. ; upon benzyl-a-naphthylamine. FABRIK. —In alcohol: greenish blue solution.—On addition of hydro- Eng. Pat. 10619%, chloric acid to the warm aqueous solution: separation of a q Ger. Pat. 609229! green iridescent crystalline precipitate.—On addition of caustic , addn. to 45268. soda to the aqueous solution: red precipitate, soluble in ether F Fr, Pat. 1893592. with an orange yellow colour and green fluorescence.—In conc. : sulphuric acid : reddish yellow solution ; green and then blue on E | ; dilution.—Dyes : tannin mordanted cotton greenish blue. Action of nitroso-dimethyl- 1890. F. BENDER. Appearance of dyestuff : green crystals.—In water or alcohol : blue aniline upon dimethyl- A. LEONHARDT & Co. solution.—On addition of hydrochloric acid to the aqueous m-amidocresol. Ger. Pat. 62367. solution: colour becomes red.—On addition of much caustic soda to the aqueous solution: bluish precipitate, soluble in ether to red solution with red fluorescence.—In conc. sulphuric acid: green solution; red on dilution with water.—Dyes: silk or mordanted cotton a brilliant greenish blue. Action of nitroso-dimethyl- 1889. F. BENDER. Appearance of dyestuff: black powder.—In water: violet black aniline hydrochloride upon A. LEONHARDT & Co. solution. —In alcohol: blue black solution.—On addition of m-oxydiphenylamine. Eng. Pat. 8264®, hydrochloric acid to the aqueous solution: blue black precipi- Ger. Pat. 5061289. tate.—On addition of caustic soda to the aqueous solution: violet black precipitate.—In conc, sulphuric acid: nearly black solution; violet black on dilution with water.—Dyes: tannin mordanted cotton blue black. Action of nitroso-dimethyl- 1889. J. R. Gerey. Appearance of dyestuff: light gray paste.—In water: sparingly aniline hydrochloride upon Eng. Pat. 294189, soluble with pale bluish colour.—On addition of hydrochloric gallamic acid, and conversion Am. Pat. 410733. acid: dissolves more readily, solution wine red.—On addition of into the bisulphite compound. Ger, Pat. 4899689. caustic soda: deep bluish violet solution.—In conc. sulphuric J. Soc. Dyers & Colorists, 1889, 170. acid: violet gray solution; wine red on dilution with water.— . Dyes: chrome-mordanted wool blue. Bromination of resorufin, 1880. |P. WusreLsky & R. BENEDIKT.| Appearance of dyestuff: brownish red solution filled with small obtained by heating nitroso- Mon. f. fe oe cae 18, ref. green crystals.—In boiling water: reddish violet solution with ? z ’ - resorcinol with resorcinol in | presence of conc. sulphuric acid. BINDSCHEDLER & BuscH. Ger. Pat. 14622® (expired). Eng. Pat. 939°. H. Brunner & Cu. KRAMER. Ber. 17, 1847, 1867, 1875. R, Nierzxi, A. Dierzn, and H. MAcKueEr. Ber. 22, 3030. J. Soc. Chem, Ind. 1890, 489. green fluorescence.—On addition of hydrochloric acid to the aqueous solution: yellowish brown precipitate.—On addition of caustic soda to the aqueous solution: no change.—In conc. sulphuric acid : the dry dyestuff gives a blue solution, which on dilution with water first becomes violet and then deposits a red- dish brown precipitate.—By zine dust and caustic soda: de- colourised, the decolourised solution becomes blue on exposure to air.—Dyes: silk and wool blue with a brownish fluorescence. 166) ag 382 Commercial Name. Lauth’s Violet. Thionine. (No longer in com- merce. ) Methylene Blue B&BG. [B.] Methylene Blue B B in powder extra D. [M] [4.] Methylene Blue B B in powder extra. [B.] [M.] [A.] Ethylene Blue.* [0.] * Ethylene Blue is a mixture of methylene blue with its conversion products, sometimes with methylene azure (cp. Bernthsen, Scientific Name. Empirical Formula. Constitutional Formula. Hydrochloride of thionine (imidamido- thiodiphenylimide). Hydrochloride (methylene blue BG, B B tin powder extra D, and printing blue) or zinc-double- chloride (methylene blue B, B B in powder extra, dyeing blue) of tetramethyl- thionine. C,H) N,SCl [1] CIH,N [4] CH, CyH, [4] NH, [2] Hydrochloride : Hydrochloride : C,,H,,N,SCl e N(CH;), Zinc-double-chloride : Ne a (C,,H,N,SCl), | C,H, + ZnCl, + H,0 N(CH,),Cl Le. [1] 49 eee C1CH,),N [4] C1, C,H,[4] N(CH,), [2] methylene blue (Meister, Lucius, & Brinins a ee A a ee ee ey ee ow (‘ethylene blue”). (c) Preparation of the thio- sulphonic acid [1] N(CHs)2 CeH34 [8] S:‘SO3sH [4] NH» by the action of thiosulphuric acid upon the oxidation-product [1] N(CHs)2Cl [4] NH of dimethyl-p-phenylene diamine, or by oxidation of dimethyl-p-phenylene diamine in presence of sodium thiosul- phate ; followed by either : 1. Conjoint oxidation of the CoH _ |thiosulphonic acid and dimethy]- aniline, by bichromate, to the insoluble compound N(CHs), | — which by boiling with aqueous zinc-chloride is converted into leuco-methylene blue, and thence by further oxidation into methylene blue ; or 2. Conversion of the thiosul- phonic acid by reduction into the corresponding sulphydrate [1] N(CH)» C,H;5 [8] SH or by acids NH into the corresponding disul- phide, and conjoint oxidation of one of these compounds with dimethylaniline to the insoluble reen indamine (C,gHjy>N,SHCl),ZnCl,, which changes into leuco-methylene blue on heating the solution, or on standing. Eng. pat. 899286; Ger. pat. 38979). : Year of Discoverer, Patents. Method of Preparation. Discovery. Literature. Oxidation of p-phenylene 1876. Ca. LAUTH. diamine in acid solution con- Bull. Soc. Chim. 25, 422. taining hydric sulphide, by A. BERNTHSEN. — means of ferric chloride. (from thiodiphenylamine. ) Ber. 17, 615, 2854, Ann. 230, 108. Bap. ANIL. & SoDA FABRIK. e Ger, Pat. 251508. (a) Treatment of nitroso- 1876. H. Caro. dimethylaniline in acid solution Bap, Antu. & SopA with hydric sulphide, whereby FABRIK. dimethyl-p-phenylene diamine Eng. Pat. 375177. and leuco-methylene blue are Am. Pat. 20479678, formed, and oxidation of the Ger. Pat. 188677. solution in presence of hydric O. MiuiHAvser. sulphide (obsolete). Ding. Pol. J. (1886), 262, 371. (b) Conversion of nitroso- J. Chem, Ind. 6, 136. dimethylaniline, dissolved in 1882. rama _ sulphuric acid (sp. gr. 1°4), by ; : eeakant with tne sulphide Eng. Pat, 4048", into leuco-methylene blue, and Am, Pat, 2/0811. oxidation of the latter Ger. Pat, 24125. 1885. E. ULLRICH. Metstrer, Lucrus, & BrRUNING. Eng. Pat. 4356 Am. Pats. 362592 & 366639. Ger. Pats. 38573"; 3975785; and 4680588, A. BERNTHSEN. Ber. 16, 1025; 17, 611, 2854, 2860. Ann. 230, 137; 251, 1. J. Soc. Chem. Ind. (1885), 4, 276 ; (1887) 6, 136; (1889), 8, 452. Bap. ANIL. & SoDA FABRIK. Eng. Pat. 10314®. Ger. Pat. 45839® and 47374°8, Kocu. Ber. 12, 592. G. ScHULTZ. Chemie des Steinkohleentheers, 1st edit., p. 1046. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: blackish green metallic glistening powder. —In water: sparingly soluble cold, easily on boiling.—On addi- tion of hydrochloric acid to the aqueous solution: colour becomes rather bluer.—On addition of caustic soda to the aqueous solution: brownish red precipitate.—In conc. sulphuric acid: yellowish green solution ; blue and then violet on dilution with water. Appearance of dyestuff: dark blue or reddish brown bronzy powder. —In water: easily soluble with a blue colour.—In alcohol: less easily soluble.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda: colour becomes more violet, a large excess gives a dull violet precipitate. —In conc. sulphuric acid: yellowish green solution; blue on dilution with water.—Reducing agents: convert it into leuco- methylene blue, which is reoxidised to methylene blue by air.— Dyes: cotton mordanted with tannin blue. ‘ Ann. 230, 169). Methylene Green extra yellowish conc. [M.] is nitro-methylene blue obtained by the action of nitrous acid upon [ 168 | : Sc | } ] No.| Commercial Name. | Scientific Name. Empirical Formula. Constitutional Formula. . ag) : 1 383) Thionine Blue pepe aes Hydrochloride : Hydrochloride : of trimethylethyl- ‘ | ss Th thionine. Cy; HyN SCI Lg Cl(CH,)(C,H,)N [4] CoH3 CoH [4] N(CH.), . [2] 384} Toluidine Blue. Oe Hydrochloride : Hydrochloride : of dimethyl- 1 LB ATM 2 toluthionine. Comics at CH Cl(CH,),N [4] CoHsCoHa Colle OgHla| Fay NH,HCl [2] —— ES ee ee eee eal : : 4 [ 169 Method of Preparation. Oxidation of the thiosulphonic acid (see No. 382) together with ethylmethyl- aniline to the insoluble green indamine, boiling the latter with zine chloride solution, and oxidation of the leuco-com- pound produced. Oxidation of the thiosulphonic acid (see No, 382) together with o-toluidine to the insoluble green indamine, boiling the latter with aqueous zine chloride, and oxidation of the leuco-compound obtained. Ethyl-p-tolylene-diamine-thio- sulphonic acid, obtained by oxidation of p-amido-ethyl-o- toluidine in presence of sodium thiosulphate, is oxidised together with ethyl-o-toluidine, and the green indamine obtained is heated. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Year of Discoverer. Patents. Discovery. Literature. 1885. E. ULLRICH. Meister, Luctus, & BRUNING. Eng. Pat. 43%. Am. Pat. 86259287. Ger. Pat. 38573®. Hr Pats Lisle: 1888. Bap. Antu. & SODA FABRIK. Eng. Pat. 10314°8. Ger. Pat. 4737488, addn. to 4583997, Mnristrer, Lucius, & BRUNING. Ger. Pat. 4734558, addn. to 4680558, Am. Pat. 416055%%, Appearance of dyestuff: reddish brown powder.—In water: blue solution.—In alcohol: less readily soluble.—On addition of hydrochloric acid to the aqueous solution: no change. —On addition of caustic soda: colour becomes more violet, an excess throws down a violet precipitate.—In conc. sulphuric acid: yellowish green solution, blue on dilution with water.—Dyes: mordanted cotton blue. Appearance of dyestuff: dark green powder.—In water: easily soluble with bluish violet colour.—In alcohol: blue solution.—On addition of hydrochloric acid to the aqueous solution: blue solution.—On addition of caustic soda to the aqueous solution : dull violet precipitate.—In conc. sulphuric acid: yellowish green solution ; blue on dilution with water.—Dyes: mordanted cotton blue. 1891. A. WEINBERG. L. CASSELLA & Co. Eng. Pat. 84079). Appearance of dyestuff: metallic glistening crystalline powder.—In water : easily soluble, violet blue when cold, pure blue when hot. —In alcohol: tolerably soluble with a greenish blue colour.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda to the aqueous solution : immediate chocolate brown precipitate.—Conc. sulphuric acid: yellowish green solution; pure blue on dilution with water.— After reduction with zinc dust: colour returns on exposure to air.—Dyes: tannin mordanted cotton blue. Sulphobenzylethyl-p-phenylene- diamine-thiosulphonic acid, obtained by oxidation of benzyl- ethyl-p-phenylene-diamine-sul- phonic acid in presence of sodium thiosulphate, is oxidised to- gether with benzylethylaniline- sulphonic acid, and the sulpho- indamine-thiosulphonate thus obtained is heated to boiling. AZINES. Eurodines. 1890. A. WEINBERG. L. CAsseLLa & Co. Eng. Pat. 4596%. Am. Pat. 434493. Employment : J. Soe. Chem. Ind. 1892, 30. Appearance of dyestuff: indigo blue powder or paste.—In water : very soluble with a pure blue colour.—In alcohol (95%) : sparingly soluble.—On addition of hydrochloric acid to the aqueous solu- tion ; no change.—On addition of caustic soda: no change in the cold, violet on heating.—In conc. sulphuric acid: grass green solution ; bright blue on dilution with water.—After reduction with zinc dust: colour returns on exposure to air.—Dyes: wool and silk blue of indigo carmine shade from an acid bath. Method of Preparation. Action of hydrochloride of nitrosodimethylaniline upon m-phenylene diamine. Year of Discoverer. Patents. Discovery. Literature. 1879. O. N. Wirt. Eng. Pat. 4846°. Am. Pat. 248246. Ger. Pat. 15272°°. Action of hydrochloride of nitrosodimethylaniline upon m-tolylene diamine. 1879. O. N. WITT. Eng. Pat. 4846°°. Am. Pat. 249136. Ger. Pat. 15272°®°, Ber. (1879) 12, 933. Ber. (1886) 19, 2604. Ann, (1886) 236, 332. Z BERNTHSEN & SCHWEITZER. Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff: greenish black powder, which is very irritating to the mucous membrane.—In water: easily soluble with violet red colour.—On addition of hydrochloric acid to the aqueous solution: scarcely any change with a small quantity, blue coloration with a large excess.—On addition of caustic soda to the aqueous solution: brown precipitate.—In conc. sulphuric acid : green solution, becomes first blue and then violet on dilution with water.—Dyes: cotton mordanted with tannin and tartar emetic reddish violet. Appearance of dyestuff: dark green powder.—In water : carmine red solution.—In alcohol: magenta red solution with slight prownish red fluorescence.—On addition of hydrochloric acid to the aqueous solution: colour becomes bluer, pure blue with a large excess.—On addition of caustic soda to the aqueous solu- tion: yellowish brown precipitate.—-In conc. sulphuric acid: green solution; blue and then magenta red on dilution with water. —Dyes : cotton mordanted with tannin and tartar emetic bluish red. ayer y | b. Safranines No.| Commercial Name. Scientific Name. Empirical Formula. | Constitutional Formula, 389| Neutral Blue. Dimethylamido- C,,H,)N,Cl f14JN [1] "1 ae (CHAN IIC HY | Cul F diloritte, i , [2] ae C,H Ales Dimethylamido- OMEN PIO a ONSITE SE henylamido-phenyl- aie (CH;).N [4] C eae a ho oH; [6] NHC,H [L.] P Nra 10'*5 65 Azine Green T O Sea ampere [2] Nie fee] d Cl C,H, % Dimethylamido- Cee clanNe Cl] ae Sa TUL toiylanidoreniy i (CH,),N [4] C,H au ie oe H,[7]NH - C,H R&BB : 3 10°75 tae : henonaphthazonium [2 Np ] [D.H.] ' i ‘oe Cl C,H, 392| Phenosafranine. | Di-amido-phenyl- Cee eNc. Cl wo C,H,[4] NH, Safranine B extra. Dep [B.] [1] x [1] HN [4] CH, cyHl NH, [2] N(2]- 7% A Cl C,H, 393 Amethyst Tetraethyl-diamido- Cy gH» N,Cl Cl ha C,H,[4] N(C,H,). : phenyl-phenazonium Violet. + [K.] chloride (No longer in com- ‘ [1] M [1] merce. ) (C,H,).N [4] C,H. C,H,[4] NH, Cl C,H,- OCH, For Haxamuple : Or CHL{S} NHL) [1] C,H ao Magdala Red. Naphthalene Red. Naphthalene Rose. Naphthalene Scarlet. Sudan Red. Rosanaphthyl- amine. [1] x, [1] (CH;).N [4] C,H.[4] NH, - HNO, 422| Benzoflavine. Hydrochloride of C,H, NHC C,H [0.] diamido-phenyl-di- = ri ° , methyl-acridine. eal oH Hcl? aN [4] NH, - HCl H,C[5]J °°? yoywpay © ®\L5] CH, | | XV. THIOBENZENYL No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 423| Thioflavine T. Dimethyl-dehydro- 0,,,,N,SC1 CH,Cl [CJ thiotoluidine-methylo- ; chloride. 2 N se CH,[4] CH

  • 0,Hy Cy > C,H, - OH, I S . SO.N CoH 2 ue 3 C.H { 3 [.] dedi ee Pad [1] | 6 3\ [4] — » = =~ — C,)H,(OH),(CO,Na) (SO,Na) | naphthoic-sulphonic- (Cake: [4] -N=N —C,)H,(OH) (S0,Na) : a-naphthol-p- *5|[8} OCH, sulphonic acid. | 437| Direct Blue R. Sodium salt of Cena NgOs, doe [3] CH | ditolyl-disazo-dioxy- sedietkae™ pak leccde 2 C,H ae | oe Goptt howulehncie [1] | Mealed nee = a a Cis) (CO2N®) Sire: a-naphthol-p- [4] -N=N —C,)H,(OH) (80,Na) sulphonic acid. 624 (3) Gia 438} Direct Brown J. Sodium salt of OT Ea Nath C,H,(CO,Na) — N=N i] mony en elisa 2, 30724 N1gV gh Ag 6 Bec . 5 NOLO, diamine-azo- benzoic *"*\ [8] -N=N -—C,H,(NH), acid. - C,H,(CO,Na) -N=N/7 439 Acid Violet Sodium salt of C,,H.,,.N,0,SNa [1] C,H,[4] N(CH,), 6 BN. bs etal tetramethyl-p-tolyl- triamido-ethoxy-tri- phenyl-carbinol- sulphonic acid. HO -C<—[1] O,H,[4] N(CH), [2] OC,H, [1] cat NHC,H, - CH, [5] SO,Na a AEN NDIX. er as tae Method of Preparation. Year of Discoverer. Patents. Behaviour with Reagents. Shade and Dyeing Properties. Fare oo Combined with Bey. NS at Method of Employment. o-Nitro- 1 mol. 1892, Socrhrk pour WINDUSTRIB | Appearance of dyestuff: brownish red powder.—In water: benzidine. salicylic acid. CHIMIQUE A BALE. sparingly soluble cold, more readily hot with a red colour.—On imo)! addition of hydrochloric acid to the aqueous solution: dark a-naphthol-p- red precipitate. —On addition of caustic soda to the aqueous sulphonic acid. solution: no change.—In conc. sulphuric acid: carmine red solution ; yellower red on dilution with water.—Dyes: wool red from an acid bath, or upon chrome mordants, the shades being fast to light and soap. 1 mol. 2 mols. dioxy- 1892. Socrirmt pour INDUSTRIE |,APpearance of dyestuff: grayish black powder.—In water : sparingly benzidine. naphthoic- CHIMIQUE A BALE. soluble cold, easily hot with a violet colour.—In alcohol : insol- sulphonic acid. uble.—On addition of hydrochloric acid to the aqueous solu- (from B-oxy- tion: bluish gray precipitate.—On addition of caustic soda to naphthoic acid the warm aqueous solution : dull violet red.—In conc. sulphuric of m.p. 216° by acid: blue solution; bluish gray precipitate on dilution with disulphonation water.—Dyes: unmordanted cotton reddish gray to bluish black and soda shades fast to light. fusion). 1 mol. tolidine. | 2 mols. dioxy- 1892. Sociitt pour L'INDUSTRIE | Appearance of dyestuff: grayish black powder.—Behaviour with naphthoic- CHIMIQUE A BALE. reagents: the same as direct gray R.—Dyes : unmordanted cotton sulphonic steel gray to bluish black shades fast to light. acid. 1 mol. 1 mol. dioxy- 1892. SocthiTh pour L'INDUSTRIE | Appearance of dyestuff: grayish black powder.—In water : easily dianisidine. naphthoic- CHIMIQUE A BALE. soluble.—In alcohol : sparingly soluble with a reddish blue colour. sulphonic acid —On addition of hydrochloric acid to the aqueous solution : + 1 mol. bluish black precipitate.—On addition of caustic soda to the a-naphthol-p- aqueous solution: reddish violet.—In conc. sulphuric acid : sulphonic acid. greenish blue solution ; violet precipitate on dilution with water. —Dyes: unmordanted cotton steel blue to black blue shades, 1 mol. tolidine.| 1 mol. dioxy- 1892. Socmrh pour L’INpDUsTRIEF | Appearance of dyestuff: bluish black powder.—In water: violet naphthoic- CHIMIQUE A BALE. solution.—On addition of hydrochloric acid : violet precipitate. sulphonic acid —On addition of caustic soda: violet red solution.—In conc. + - mol; sulphuric acid : blue solution.—Dyes : unmordanted cotton black a-naphthol-p- violet. sulphonic acid. 1 mol. Bismarek 1892. Socrtrh pour L’? INDUSTRIE | Appearance of dyestuff: reddish black powder.—In water : yellowish m-amido- Brown. CHIMIQUE A BALE. brown solution.—In alcohol: sparingly soluble.—On addition of benzoic acid. hydrochloric acid to the aqueous. solution ; brown precipitate. —On addition of caustic soda: little change.—In conc. sulphuric acid: brown solution; brown precipitate on dilution with water. —Dyes: unmordanted cotton yellowish brown. Sulphonation of tetramethyl-p- 1891. Sociith PouR L’ INDUSTRIE | Appearance of dyestuff: dark violet powder.—In water: violet blue tolyl-ethoxy-tri-phenyl-carbinol obtained by condensation of tetra-methy1-diamido-benzo- phenone chloride with m-ethoxy-phenyl]-p-tolyl-amine. CHIMIQUE A BALE. . Bap. ANIL. & Sopa FABRIK, solution.—On addition of hydrochloric acid : blue precipitate.— On addition of caustic soda: bright blue solution, colourless with an excess.—In conc. sulphuric acid: brownish yellow solu- tion ; green and finally blue on dilution with water.—Dyes: wool and silk bluish violet. No.| Commercial Name. Scientific Name. Empirical Formula. Constitutional Formula. 440| Acid Violet 7 B. Sodium salt of C.,H,,N,0,S,Na, [1] C,H,[4] N(C,H,) [7] [B.] Danae HO -C<[1]0,H,[4] N(CHC,H, -S0,Na phenyl-carbinol-di- [1] CsH,[4] N(CH, iG, tie SO; Na sulphonic acid. 441} Wool Green S§. Sodium salt of Cy,HogN.0,8,Na, [1] C,H,[4] N(CH,), [ T] [B.] tetramethy1-di-amido- TO ee [ 1]C.H [ 4] N(CH,), B-oxy-naphthyl- 64 3/2 | carbinol-di-sulphonic [1]¢,,H Ee OH acid. ae (SO,Na), 442 Indoines. pec cemonas of For instance - For instance « [B.] safranine-azo- Cen NOC | naphthols. ge azo NELLAIO Hy < oy CoLLAIN = NIC 201 Cl C,H, 443 Roxamine. Sodium salt of Ci High Oso [D.H.] diony-azo-naphthal- | 929" “oe {hy Non [1] Cy gH tees i ene sulphonic acid. 10 Bie OH 444| Benzo Indigo Sodium salt of C.,H,)N,O,Na CH, [4] aa = [4] C,,H,[1] NH, Blue. diethoxy-diphenyl- [3] 0 [By.] disazo-a-naphthyl- [1] le [3] Oo ; amine-dioxy- C,H At 1}0H naphthalene- [4] N= oN [4] CjpH,(SO,Na) td OH sulphonic acid. 445 | Victoria Black B.* Sodium salt of C.gH,.N,0,S,Na, CH [4] SO,Na [By.] p-sulphobenzene-azo- 6 4\ [1] N=N[1] : a-naphthalene-azo- 4iNa Nis > C,H, dioxy-naphthalene- [4] Neat sulphonic acid. C,H [1] OH 4) (8) Of SO.Na 446, Chromatropes 2 R, 2 B, 6 B, 8B, &10B [M.] 447, Chrome Violet. | Hydroxy or carboxy E.g. Chrome Green : Chrome Blue. derivatives of tetra- [1] C,H,[3] CO,H Chrome Green. pote Mert HO-C< [1] C,H,[4] N(CH,), [ By.] diphenylnaphthyl- [1] CgH,[4] N(CH,), earbinol. 448 Anisolines. Bethy) a eux For wnstance - For «instance : thers o e 1 [Mo.] ore CygHo,N,0,C1 C\(CH,)oN :[4] C,H

    Cole L4 NHO,H, | C,H, Probably : [1] C,H, [4] NHC,H, HO-C [1] C,H, (SO,H), [3] OH - [1] C,H, [4] NHC,H, N — C,H, (CH,) -N=N —[2]C,,H, [1] N - C,H,(CH,) -N=N-[1]C,,H, “ N — C,H, (CH,) —N=N - [2] C,H, | ee N — C,H,(CH,) - N=N — [1] C,,H, [2] OH Behaviour with Reagents. Shade and Dyeing Properties. Method of Employment. Appearance of dyestuff : light maroon coloured powder.—In water : red solution with an orange fluorescence which disappears when hot.—On addition of hydrochloric acid to the aqueous solution : pink precipitate.—On addition of caustic soda: no change.—In conc. sulphuric acid : orange solution ; red precipitate on dilution with water.—Dyes : wool a very blue red from an acid bath, with or without a chrome mordant, the colour being fairly fast to alkalies, light, ete. MBISTER, Lucius, & Brunina.| Appearance of dyestuff: maroon powder.—In water : reddish violet solution. —On addition of hydrochloric acid to the aqueous solution: purple precipitate.—On addition of caustic soda: cherry red solution.—In cone. sulphuric acid: reddish orange solution ; reddish violet precipitate on dilution with water.— Dyes : wool violet in the same way as the preceding. Appearance of dyestuff: purple powder.—In water: bright blue solution.—In alcohol: slightly soluble with a blue colour.—On addition of hydrochloric acid to the aqueous solution: blue precipitate.—On addition of caustic soda : violet precipitate.—In conc. sulphuric acid: bluish green solution ; becoming blue and bluish violet on dilution with water.—Dyes : silk blue with a red fluorescence. Is faster to light than the ordinary indulines. Appearance of dyestuff: dark blue powder.—In water: easily soluble to a bright blue solution.—On addition of hydrochloric acid to the aqueous solution: colour becomes green and then yellow.—On addition of caustic soda: dichroic green red solu- tion, becoming wine red on boiling.—In conc. sulphuric acid: yellow solution ; green and finally blue on dilution with water.— Dyes: wool a pure blue from an acid bath. Employed as a substitute for indigo-extract in wool dyeing. Appearance of dyestuff : dark red powder.—In water: easily soluble to a scarlet solution.—In alcohol: insoluble.—On addition of hydrochloric acid to the aqueous solution: no change.—On addition of caustic soda: orange red solution.—In cone. sul- phuric acid : bluish red solution ; scarlet on dilution with water.— Dyes: wool from an acid bath a bright scarlet, which is very fast to milling and scouring. : : Year of Discoverer. Patents. fo eoe oF Freparation. Discovery. Literature. Action of o-toluidine upon 1888. MerstEr, Lucius, & BRUNING. fluoresceine chloride, and Eng. Pat. 96008, sulphonation of the product. Action of p-toluidine upon 1888, fluoresceine chloride and Eng. Pat. 9600°. sulphonation of the product. | By heating benzene-azo-a- 1891. KALLE & Co. naphthylamine with a-naph- Ger. Pat. 62179. thylamine hydrochloride and O. Fiscozer & E. HeEpr. aniline, and sulphonation of Ann. 272, 306. the product. H. von PERGER. J. Soc. Chem. Ind. 1892, 30. Condensation of m-oxybenz- 1891. A. WEINBERG. aldehyde with ethyl-o-toluidine L. CASsELLA & Co. sulphonation of the leuco base Eng. Pat. 15143%. and oxidation of the sulphonic acid obtained. Combination of 1 mol. of 1889. A. F, Porrrizr, and diazotised di-m-amido-azoxy- D. A. RosENSTIEHL. toluene with 1 mol. of a- Ger. Pat. 51363. naphthol-mono-sulphonic acid Brooks, Simpson, & NW and 1 mol. of 6-naphthol- SpruuerR, Limd. disulphonic acid R. Eng. Pat. 10915”. at Combination of 1 mol. of 1892. A. G. GREEN. diazotised di-m-amido-azoxy- toluene with 1 mol. of a- naphthol-mono-sulphonic acid NW and 1 mol. of 6-naphthol. Brooks, SIMPSON, & SprLLeR, Limd. Eng. Pat. 19891. Appearance of dyestuff: red powder.—In water: very sparingly soluble.—In alcohol: insoluble.-—On addition of hydrochloric acid to the aqueous solution : scarlet precipitate.—On addition of caustic soda : orange red solution.—In conc. sulphuric acid : bluish red solution; scarlet precipitate on addition of water.— Dyes: wool a bright scarlet from an acid bath, and is extremely fast to milling and scouring. : woynypos plow ormoryo ZT YAM Surzj0ds uo surnyor qnq ‘iTe 0} atnsodxe uo ‘T[v 4v you 10 ‘A,MoTs Ar9A stvaddvar M0Too oY, "8.4N070)-aUIpwop pure ‘-ou1zny J ‘-aurewxgQ ‘-owizpy : ie 04 ainsodxe uo savoddver ATYyomnb AMo]Oo [VULsIIO OTL, “MOTINPOS prow ormorys 77 Jo dorp v YA peyono, st yods oxy “Are 07 etnsodxe uo uNyor Appmb jou seop mojoo ey} Jy ~«aodvd 109, y wo 4nd uorynqos pastanoposep ayy Jo dozp ve pure ‘prow orz0TYyorpAY pue ysnp outz YIM poonper st UoTNTos snoenbe oyy, ‘sunopoyn asng 3 uoynjos uiuung ha paynpdwag "W ‘IOVOM UI oTqnToy synqysefq—']T dnoiy ‘SoTe} OY} UL ToquMuU s}t Sutoq IMopoo Yows ysurvse equ ot} ‘sopqe} Surose10y oy} UL WUINTOd 4seT oY} 208) serytodoid Surekp soy} Lq pue “ozo ‘oyooyr “prov otmmydins ‘ouoo ‘serveyye pue sproe snoonbe spresao} IMorvyoq aeyy Aq Joyo Yove Woy poystuSurystp ore dnois oures oy} Jo sioquiom oy, - syuahvae burysenburysr Pay el eA Pe I nee ee eros ade teat 2 Pome sryerr 17 J ¢ LL + $? 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ACETANILIDE, 14 Benzylaniline, 24 Dichloro - 0 - nitro - benzaldehyde, Alphanaphthol, 38 Benzyl chloride, 49 , 50 Alphanaphthylamine, 18 Benzylidene dichloride, 49 Dichlorophthalic acid, 13 Amidoazobenzene, 54 Beta-naphthylamine, 21 iis anhydride, 13 a-Amidoazonaphthalene, 55 Binitrobenzol, 7 p-Diethylamidobenzaldehyde, 51 Amidoazonaphthalene Binitrotoluol, 8 Diethyl-m-amidophenol, 46 disulphonic acid, 54 Bitter almond oil, 49 Diethylaniline, 26 Amidoazotoluene, 54 Diethyldibenzyldiamido- Amidoazoxylene, 55 CARBAZOLE, 27 diphenylmethane disulphonic m-Amidobenzaldehyde, 51 Carbolic acid, 6 acid, 30 Amidobenzenylamidothiocrésol, Carbonyl chloride, 56 p-Dimethylamidobenzaldehyde, 31 m-Chlorobenzaldehyde, 50 51 o & m-Amidobenzoic acid, 15 Cinnamic acid, 14 p-Dimethylamidobenzophenone, p-Amidodiethylaniline, 26 Cresols, 6 52 p-Amidodimethylaniline, 25 Cresol-carboxylic acids, 36 Dimethyl-m-amidophenol, 46 a-Amidonaphthalene, 18 Cresotic acids, 36 Dimethylaniline, 25 B-Amidonaphthalene, 21 Cresylic acid, 6 Dimethylaniline sulphonic acid, Amidonaphthols, 47 and 48 w-Cumidine, 18 25 Amidonaphthol sulphonic acids, Dimethyl-a-naphthylamine, 26 47 and 48 DEHYDROTHIO-p-TOLUIDINE, 31 Dimethyl - p- phenylenediamine, m-Amidophenol, 46 Dehydrothio - » - toluidine 25 p-Amidophenol carboxylic acid, 47 sulphonic acid, 31 m-Dinitrobenzene, 7 o-Amidophenol-ethyl ether, 46 Dehydrothioxylidine, 31 a-Dinitronaphthalene, 9 o-Amidophenol-methyl ether, 45 Dehydrothioxylidine sulphonic m-Dinitrotoluene, 8 Amidosalicylic acid, 47 acid, 31 m-Dioxybenzene, 386 Amidotoluenylamidothio- Diamidoazotoluene, 35 Dioxynaphthalenes, 43, 44 and 45 xylenol, 31 Diamidoazoxytoluene, 35 Dioxynaphthalene sulphonic Amido-p-xylene, 17 m & p-Diamidobenzene, 28 acids, 43, 44 and 45 Aniline, 14 Diamidocarbazol, 34 Dioxytartaric acid, 57 o-Anisidine, 45 Diamidodimethoxydipheny], Dioxytoluene, 37 Anthracene, 5 33 Diphenylamine, 24 Anthranilic acid, 15 Diamidodipheny], 32 Dipheny] - (2 : 7) - naphthylene- Anthraquinone, 53 Diamidodiphenylamine, 31 diamine, 29 Anthraquinone sulphonic acids, Diamidodiphenylene ketoxim, 34 Diphenyl-m- phenylenediamine, 53 Diamidodiphenylene oxide, 33 29 Azobenzene, 7 Diamidodiphenylethylene, 34 Disulphobenzene-azo-a-naphthyl- Azotoluidine, 35 Diamidodiphenylmethane, 30 amine, 55 Azoxybenzene, 7 Diamidodiphenyl-urea, 34 Di -p-tolyInaphthylenediamine, Azoxytoluidine, 35 Diamidoditoly], 32 30 Diamidoditolylmethane, 30 Di-p-tolyl-m - phenylenediamine, BENZALDEHYDE, 49 Diamidoethoxydiphenyl, 33 29 Benzal chloride, 49 a-Diamidonaphthalene, 35 Benzene, 4 Diamidonaphthalene disulphonic ETHOXYBENZIDINE, 33 o-Benzenedicarboxylic acid, 13 acids, 35 Ethylbenzylaniline, 25 m & p-Benzenedisulphonic acid, 10 Diamidophenyltolyl, 32 Hi sulphonic Benzenemonocarboxylic acid, 12 An 33 acid, 25 Benzenemonosulphonic acid, 10 Diamidostilbene, 34 Ethyl bromide, 57 Benzidine, 7 and 32 Be disulphonic Ethyl-8-naphthylamine sulph- Benzidine sulphonic acids, 32 acid, 34 onic acids, 26 Benzidinesulphonesulphonic Diamidotoluene, 29 . acids, 32 Dianisidine, 33 Benzoie. acid, 12 Diazobenzene chloride, 538 FORMALDEHYDE, 56 Benzol, 4 m & p-Diazobenzene sulphonic acid, 15 Benzotrichloride, 49 Dichlorobenzaldehyde, 50 GALLIo ACID, 37 HYDRAZOBENZENE, 7 Hydrazotoluene, 8 ISOQUINOLINE, 27 METHYL-ALCOHOL, 56 o-Methylbenzidine, 32 m-Methylbenzidine, 33 Methylbenzylaniline, 24 Methylbenzylaniline sulphonic acid, 24 Methyl chloride, 57 Methyldiphenylamine, 24 Methyl-6-naphthylamine sulphonic acids, 26 Methylquinoline, 27 Monoethylaniline, 25 Monomethylaniline, 25 NAPHTHALENE, 5 Naphthalene disulphonic acids, 11. Naphthalene acids, 11 Naphthalene tetrasulphonic acid, 12 monosulphonic Naphthalene trisulphonic acid, 12 a-Naphthol, 38 B-Naphthol, 41 a-Naphthol-carboxylic acid, 38 a-Naphthol-disulphonic acids, 39 B-Naphthol-disulphonic acids, 42 a-Naphthol-monosulphonie acids, 38 B-Naphthol-monosulphonic acids, 41 a-Naphthol-trisulphonic acids, 41 B-Naphthol-trisulphonic acids, 43 a-Naphthylamine, 18 B-Naphthylamine, 21 a-Naphthylamine - disulphonic acids, 20 B-Naphthylamine - disulphonic acids, 23 a-Naphthylamine - monosulphonic acids, 19 $-Naphthylamine - monosulphonic acids, 22 a-Naphthylamine - trisulphonic acids, 21 Naphthylene diamine, 35 00a Naphthylene - diamine - disul- phonic acids, 35 m-Nitraniline, 9 p-Nitraniline, 10 o & m-Nitrobenzaldehyde, 50 p-Nitrobenzaldehyde, 51 Nitrobenzene, 7 Nitrobenzol, 7 p-Nitrobenzylchloride, 49 a-Nitro-naphthalene, 9 p-Nitroso-dimethylaniline, 25 Nitroso - dimethyl - m - amido- phenol, 46 o & p-Nitrotoluene, 8 p-Nitro-o-toluidine, 10 Nitrotoluol, 8 a-Nitro-m-xylene, 9 Nitroxylol, 9 ORCINOL, 37 Orthotoluidine, 16 m-Oxybenzaldehyde, 52 o & p-Oxybenzaldehyde, 51 o-Oxybenzoic acid, 36 m-Oxydiethylaniline, 46 m-Oxydimethylaniline, 46 m-Oxydiphenylamine, 46 Oxymethylene, 56 a-Oxy-8-naphthoic acid, 38 Oxy-naphthylamines, 47 Oxytoluic acids, 36 PARATOLUIDINE, 16 o-Phenetidine, 46 Phenol, 6 Phenol-o-&--sulphonic acids, 36 Phenylacrylic acid, 14 m-Phenylamido-phenol, 46 Phenylamine, 14 m & p-Phenylenediamine, 28 m-Phenylenediamine sulphonic acid, 29 Phenylglycocol, 14 Phenylglycocol-carboxylic acid, 15 Phenylhydrazine sulphonic acid, 16 Phenyl-a-naphthylamine, 26 Phenyl-8-naphthylamine, 26 Phosgene, 56 Phthalic acid, 13 Primuline base, 31 Pyrogallic acid, 37 © Pyrogallol, 37 QUINALDINE, 27 Quinoline, 27 RESORCINOL, 36 SALICYLIC ACID, 36 Salicylic-acid - azo-a - naphthyl- amine, 55 Succinic acid, 57 m & p-Sulphanilic acid, 15 Sulpho- - naphthalene - azo - a- naphthylamine, 55 Sulpho-p-toluene - azo-a- naphthylamine, 55 TETRACHLOROPHTHALIC ACID, 13 Tetrachlorophthalic anhydride, 13 Tetraethyldiamido- benzophenone, 52 Tetramethyldiamido- benzophenone, 52 Tetramethyldiamidodiphenyl- carbinol, 30 Tetramethyldiamidodiphenyl- methane, 30 Tetramethyldiamidothio- benzophenone, 52 Tetrazodiphenyl chloride, 32 Thiocarbonyl chloride, 56 Thiophosgene, 56 Tolidine, 8 and 32 Toluene, 4 o & p-Toluidine, 16 o-Toluidine-m-sulphonic acid, 17 p-Toluidine sulphonic acids, 17 Toluol, 4 o & p-Tolyl-m-amidophenol, 47 m & p-Tolylenediamine, 29 m-Tolylenediamine sulphonic acids, 29 p-Tolyl-a-naphthylamine, 27 p-Tolyl-8-naphthylamine, 27 Woop Spirit, 56 XYLENE, 4 Xylidines, 17 Xylidine-sulphonie acid, 18 Xylol, 4 : | : 2 : (The Numbers refer to the position in the tables ; AcETIN BuuE [B.], 402 Acid Brown G [A.], 145 » Brown R[A.], 91 » Cerise [M.], 301* ., Fuchsine [.], 301 ,, Green [C.], 288 ” ” [By. } 289 » » [By] [C.], 290 55 » SOF, 290 » Magenta [B.], 301 ,, Maroon, 301* 5, Ponceau [D. H.], 92 » Roseine, 381 » Rubine, 301 » Violet 4 BN [B.], 312 6 B[By.], 312 [¢.) 315 ” ” G, 20 Acme Yellow ae 15 il Acridine Orange [Z.], 420 » Red 3B [Z.], 284 » Yellow [Z.] 419 Aldehyde Green, 416 Alizarine No. 1. [1/.] [V.], 265 » No. 6 [Af.] 268 eNO. 10) [EV.] 266 » FA[L. & S], 266 mee bale. & S.), 265 & GI) [B.], 267 extra [By.|, 267 -|, 265 [B.], 265 a MWOSH RVI AG NY Suleee 80S. 274 » X[By.], 266 » Black S [B.], 268 » Blue [B.] [M1], 276 : » B&G W[By.], 276 ” » S[B], 277 Bordeaux B [By.], 270 * Carmine, 274 » Cyanine G [By.], 272 or ” R [By.], oA ‘3 Green 8 [B.], 279 Ap ». 063 ” » 9364 » Indigo Blue § [B.], 278 ad Maroon [B.], 275 . Orange, 273 3 mee Ae PB: |) (12), 27 - Powder W [By.], 274 , Red S[B], 274 SASRORNWrWwWHDNOOW ~~ Doha Hop a ey Dam Qo [ep] _ Ss © lar) [or] COLOURING MATTERS Alizarine Violet, 362 0 Yellow A [B.], 259 C {B.], 260 GG [M.], 33 R [AL], 34 Alkali Blue [B.S.S.] [A.] [B.] [By.] [C.] [Z.] [14.], 327 i Bee DE LAs] 822 Fi » X&G[B.S.S.], 329 » Brown D, 103 », Green [B.S.S.], 293 » Red D, 181 » Violet [B.], 331 Yellow R [D.], 188 Alphanaphthol Orange, 72 Alpine Blue [G..], 313 Alsace Green, 254 Amaranth [J/.] [C.], 89 4 Amethyst Violet [X.], 393 Anileine, 398 Aniline Black; 430 » Blue, spirit soluble, 326 Green, 416 » Orange, 2 » Pink, 395 » Purple, 398 » Red, 300 » Violet, 398 Yellow, 19 Anisidine Scarlet, 54 Anisoline [ Mo.], 448 Anisol Red, 54 Anthracene Blue [B.], 272* n Brown [B.] [J/.] [By.], 269 = Green, 363, 364 ss Violet, 362 7 Yellow [By.], 262 Anthracite Black B[C.], 148 Anthragallol, 269 Apollo Red [G@.], 39 Archil Substitute G [A.], 37 V [4.] [P.], 36 ” ” 3 VN [PJ [4.],°38 * extra [C.], 39 Artificial Indigo [B.] [1Z.], 410 : » Carmine, 411 » Extract, 411 Atlas Orange [B.S.S.], 73 » Red [B.S.S.], 104 Auramine, 281 rs O [B.], 281 Aurantia, 13 Aureoline [R.H.], 425 Aureosine, 344 Aurine, 335 OO Aurotine [Cl. Co.], 341 Azaleine, 300 Azamine 4 B, 208* Azarine 8 [Jf], 112 Azindone Blue G & R, 405 Azine Green G B [Z.], 390 » LOT[L.], 390 Azo Acid Rubine [D.], 85 ” ” ” ” ” 99 Cle Black e144" [aM], 144 2D those with (*) are in footnotes.) Azo Blue [By.] [A.], 206 5, Carmine [B.], 407 », Coccine 7 B[A.], 114 » 2R[A.], 44 Azodipheny] Blue, 402 Azoeosine [ By. |, 55 Azofiavine [B.], 108 Azofuchsine B [By.], 249 oF G [By.], 250 Azo Green [By.], 295 » Mauve [0.], 224 Azonigrine [G.], 140 Azoorseilline [A.] [By.], 173 Azorubine A [C.], 8 6 § [4.], 85 Azo-Turkey-red, 67* » Violet [By.], 233 » Yellow [dZ.], 108 Azuline, 320 Azurine, 320 ” [B.], 367 BASLE BLuE R & B B[D.H.], 391 Eis, BIB Sasol Bavarian Blue, spirit soluble [A.], 321 2 Pe DB RY RAR eS 24: ee DSre PAR esas Benzal Green, 285 Benzoazurine G [By.], 232 % 3 G [By.], 235 .Benzo Black Blue G [By.], 246 ” » R[By.], 247 Benzo Brown B [By.], 242 Gr By. 24ll Benzoflavine [O.], 422 Benzo Gray [By.], 248 » Indigo Blue [By.], 444 » Orange R [By.] [A.], 187 Benzopurpurine B [By.] [A.], 210 i 4 B [By.] [A.], 208 : 6 B[A.] [By.}, 209 as 10 B [By.], 236 Benzoyl Green, 285 Benzyl Violet, 307 Betanaphthol Orange, 73 Biebrich Scarlet, 129 Bismarck Brown, 149 Bitter Almond Oil Green, 285 Black Paste, 378 Bleu-de-Lyon, 326* Bleu-de-nuit, 326 Bleu-de-Paris, 326* Bleu Fluorescent [/.], 380 » Lumiére, 326 » Marine, 328 Blue Black B [B.], 144 ” » KR, 144* » Fine, 326 Bordeaux B [A.], 65 % B X [By.], 125, 135 _ CO V [A.], 174 a G [By.], 134 ” S [A. 1, 89 Extra [By.], 174 Bradford Blue [B.S.S.], 333 Brahma Orange [Z.], 190 » Red B&BB[Z], 189 » » 6 B[Z], 191 Brilliant Azurine 5 G [By.], 238 Brilliant Black B [B.], 142 Congo G [A.] [By.], 179 yg, BEAL) [By.], 212 % Cotton Blue, greenish [By.], 325 a Croceine [C.] 117 . Green [B.] [By.] [C.] LAC], 286 Hessian Purple [Z.][A.] [By.], 166 3 Orange [/.], 26 4s Ponceau 4 R [By.], 95 Ps Purpurine [A.], 220 5 Scarlet [C.], 88 Double G [A.], 94 » oR [By], 95 . Yellow [Sch.], 11 i » [LZ] [A.] [By.], 162 ite LE se Brown NP&NPJ [D.H.], 35 Buffalo Rubine [Sch.], 61 Butter Yellow, 29 ” ” CacHou-DE-LAvaAL [P.], 481 Canarine [D. H.], 427 Capri Blue [Z.], 377 Carbazol Yellow [B.], 200 Carbazotic Acid, 1 Cardinal, 30* > Red §, 301* Carminnaphth, 67 Carmoisine [By. ], 85 Carnotine [ CU. Co.], 425 Catechu Brown [A.], 243 Ceracine, 84 Cerise, 801* » _[C.], 800* China Blue [B.S.S.] [A.] [By. i 328 Chloramine Yellow [ By.], 426” Chlorin [ D.#.], 254 Chrome Blue [ By.], 447 » Green [By.], 447 5 Violet, 398 ” » [By.], 447 » . \Realh BBE Chromine G & R, 424 Chromotropes [ M.], 446 Chrysamine G | By.] [A.], 180 » B [By] [A], 214 Chrysaniline, 421 Chrysaureine, 73 Chryseoline, 71 Chrysoidine, = R [C.], 30% Chrysoine wari eal Chrysoline [Jo.], 343 Chrysophenine [Z.] [A.] [By.], 164 Cinnamon Brown, 149 Citronine, 107 : Citronine [B.S.S.], 12 A [Z.], 10 Clayton Cloth Brown [CZ. Co.], 105 <5 » Red [Cl. Co.], 102 Wool Brown [CZ. Co.], 153 >, Yellow [Ci. Co.], 99 Cloth Brown G [By.], 186 ey ole eae ,, Orange [By.], 184 » Red B[O.], 122 B [By.], 123 3 B extra, 123* G [By.], 114 G [0.], 121 G extra [By.], 121 » 3G extra [By.], 124 Coccine, New [A.], 64 Coccinine [1Z.], 53 “ B [MM], 56 Cochineal Red A [B.], 88 * Searlet G [Sch.], 25 99 99 ” 2? ” f 202 ] Cochineal Red 2 R[Sch.], 40 » 4R[Sch.], 45 Ceruleine [B.] [By.] [12], 363 93 8 [B.] [By.] [AL], 364 Congo G [A.] [By.], 176 x) We CATR pe , Brown G [A. ], 240 ” ” R [A.], 239 » Corinth B [By.] [A.], 207 » » GA.) [By], 175 » Orange R[A.], 221 Setved [PAs iil afedaliant ” ” a: R [A.] [By.], 213 » Violet [A. ], 174 Yellow in paste [A.] [By.], 172 Coraline, 337 Cotton Blue [Z.], 328 » Blue, non-mordant [B.S.S. ], 329 % ee Ba, Bile » Bordeaux [B.], 204 Sr eed (B3),.205 » Scarlet pao 117 ” » [B.K.], 156 Yellow G [B. ih abate) Coupier’ s Blue, 402 Cresol Red [B. , 57 Croceine, 128 7 B [Sch. ], 115 5 3 B [Sch.], 120 j 3 BX [By.], 86 < Brilliant [C.], 117 5 Orange [By.] [K.], 26 + Scarlet 7B [By.], 133 Crystal Ponceau [B.], 64 » scarlet 6 R[C.], 64 » Violet [B.] [Z.], 804 Cumidine Ponceau, 51 5 Red, 51 Curcumeine, 79 53 [A.], 107 Curcumine § [Z.], 15 Cyanine, 414 Cyanosine, a BZ], 356 Cyclamine [ Mo. ], 361 Danita, 303 % 809 Dark Green [B.], 254 Deep Red [Cz.], 59 Deltapurpurine 5 B [By.][A.], 211 Fe 7 B[By.][A.} 219 G [By.], 178 ; Diamine Black B [C.], 229 5 ay Cale 198 = Blue B [C.], 227 BB[C.], 197 ” ” a . Black E [C.], 280 Be Bronze G[C.], 198 55 Brown V [C.], 195 93 Fast Red [C.], 194 “4 Gold [C.], 160 “ Green B [C.], 199 - Red B [A.] [By.], 211* 3 B[C.] [A.] [By.], 219 + se) OUGE 225 = Scarlet B [C.], 183 » Sky Blue [C.], 237 f Violet N [C.], 196 3 Yellow G [By.], 252 eee NG 226 Diamond Black [By.], 139 = Green B [B.], 285 D Yellow R [By.], 253 Dianthine, B, 350 i G, 351 Dimethylaniline Orange, 74 ” ” | Dinitrosoresorcin, 254 Dioxine [Z, ], 257 Diphenylamine Blue, 324 spirit soluble or opal, 321 - Orange, 75 Direct Blue, 321 B [Z.], 486 9 ” R [/. ] 437 , Brown J [/.], 438 » Gray B[Z.], 435 » _» RL] aoe » Red [A.] [By.], 203 [G.], 281 = » B[LW.N.], 183 » Violet, 303 » Yellow [A.] [By.], 202 Double Brilliant Scarlet G [A.], 94 3 R[By.], 95 ” ” ” ” ” ” ” ” 5 Green [K.], 305 » Scarlet LK. ], 127 » . ExtraS[A.], 95 Dragon Green, 285 ECHURINE, 1* Eclipse Red, 208* Emerald Green [By.], 286 English Brown, 149 A Yellow, 2 Hosine [ B.], 346 » A LBa846 , A extra [.D.H.], 346 » 3B, 346 » B{Z£.], 349 » BB[L], 348 » BN[B], 349 >. BWrisdo » GGFE[C], 346 » a G (Ca e46e » . J LB] 23b0 » oJ and 4J extra [Z.], 346 » S[B] 348 » aJlaleool, 348 » bluish, 350 » Orange |Jil.346° » scarlet B[C.], 349 », Water Soluble [J/.], 346 Yellowish [A.] [B.S.S.], 346 Erika B [A.], 69 Erythrine, 347 5 X [B.], 119 Erythrobenzin, 300 Erythrosine [B.] [12] [B.S.S.], 350 - B[A.], 3 - B [ZL], 855 2 D [C.], 350 G [B.], 351 Ethylene Blue [0.], 382 Ethy] Eosine, 348 » Green, 311 ” ” [A.], 286 » Purple 6B, 310 5 Violet [B.] [Z.], 310 Eupittonie acid, 338 Extra Double Scarlet § [A.], 95 : Fast Actp Viouets [J7.], 449 , Black [Z.], 378 » Blue [B.8.8.], 327 B [A.] [By.], 403 B, spirit soluble [A.], 402 2B, for cotton [A.], 372 R [4.] [B.] [C.], 408 R for cotton, in crystals [A.], 372 R spirit soluble [A.], 402 3R [C.], 403 Black [Z.], 378 ; Greenish [B.], 403 my Brown [ By.], 148 oD} ” Fast Brown [J/.], 80. 3B [A.] 93 G [A.] [7.10], 147 » » N[B], 83 5, Green, 254 [C.], 285 [ By.], 808 J [Mo.], 286 extra [ By.], 308 i » extra bluish [By.], 308 . Myrtle Green, 254 », Neutral Violet B[C.], 399 » New Blue for cotton, 404 » Ponceau B [B.], 129 ” ” ” ” ” ” 3 POR eB LB), 180 Red, 84 9 ” [A.], 87 » » A[B.], 84 me SLD.) 65 » » BY [By.], 62 ee CIA) 85 pees 8.) 89 E [B.] [By.], 87 * EB[B.], 89 se Scarlet, 127 ” » _ 208* » Violet [D.H.], 368 B [ By.], 188 ” ” R [By.], 136 . » Yellow [B.], 21 [B.} [By.], 20 [B.S.S.], 75 Extra [By.], 20 G [K.], 20 » N[P.], 79 R [A], 21 Fine Blue, 326 Flavaniline [M/.], 412 ee O24), 413 Flavaurine, 3 Flavophenine [B.], 180 Fluoresceine, 342 Fluorescent Blue [/.], 380 Formyl Violet S$ 4B [C-.], 315 Fuschia [7.], 393* Fuchiacine 8, 300 Fuchsine [B.] [By.] [Af] [C-], 300 4 8 [B.], 301 ” ” GALLAMINE BLUE [G.], 379 Gallanilic Indigo PS [D.Z.], 371 r Violet BS [D.H.], 370 Galleine [B.] [By.] [AL], 362 Gallocyanine, 368 Galloflavine [ B.], 264 Gambine R [ H.], 255 Ye Ae, 256 Garnet [D.H.], 67 » Brown, 14 » soluble, 14 Gentian Blue 6B [A.], 326 Geranium [C.], 300* Giroflé [D.H.], 396 Gladioline O, I, and II, 179* Gold Orange [By.], 73 » Yellow [By.], 71 Green-in-paste, 306* Greenish Blue [J/.], 327* » Powder, 305 Grenadine, 301* Grenat, 300* SEL DaLeoOL” Guernsey Blue, 328* Guinea Green B [A.], 291 » » BV [4A,], 292 HARMALINE, 300 Helianthine [B.], 74 Heliochrysine, 9 Heliotrope [By.], 234 f 303°) Helvetia Green [/.], 288 Hessian Blue [Z.], 326 " Brown BB [Z.], 244 ‘ » MM[LZL.], 245 » Purple B [Z.][A.] [By.], 167 D[Z.] [A.] [By.], 168 99 se NEL | EA By a1 65 » Violet [Z.] [A.] [By.], 170 » Yellow [Z.] [A.] [By.], 169 Hochst New Blue [1/.], 332 Hofmann Violet [B.S.S.], 309 ” ” IMPERIAL RED, 208* Scarlet [By.], 129 u Yellow, 13 Indamines [1Z.] [ W.N.], 405 Indazine M [C.], 400 Indian Yellow [By.], 108 Indigen D & F [By.], 402 Indigo, 410 ay oxtract, 41m Indisine, 398 Indoines [B.], 442 Indophenol [D.H.], 365 is White [D.H.][C.], 366 Induline [By.] [B.S.S.], 403 Fr 3 B, 403 - 6 B 403 * Opal, 402 ‘ 3 B Opal, 402 * 6 B Opal, 402 93 Soluble, 403 5 spirit soluble [B.] [By.], 402 fp 3 B, spirit soluble, 402 : 6 B, spirit soluble, 402 NN [B.], 403 Todeosine B, 350 ey G, 351 Todine Green, 306 » Violet, 809 Isorubine [.], 300* JAUNE ACIDE, 20 » aniline, 19 7 Gore S » Orient, 351 » resistant au savon [P.], 98 », soleil, 15 Solide N, 79 Jet Black R [By.], 187 KERMESIN ORANGE [Z.], 78 LANCASTER YELLOW, 58 Lauth’s Violet, 381 Leather Brown, 149 , » [0.], 150 5 Yellow, 421 Light Green, 305 5, 290 3 » 98 F, bluish [B.], 289 » © F, yellowish [B.], 290 London Blue, extra [B.S.S.], 328 Lutécienne, 73* Luteoline, 82 Lydine, 398 ” ” MaGpALA Rep, 397 Magenta [R.H.], 300 Maize, 15 Malachite Green [A.], 285 Ag 5 BL Bie28b: = 3 GOLBi 286 3 » spirit soluble [A.], 285* Manchester Brown, 149 an 3) 2 HEC 52 7 Yellow, 8 Mandarin G extra [A.], 73 b GR [A.], 78 Maroon, 300* x 8 [B.], 301* Martius Yellow, 8 Mauve, 398 A Dye, 398 Mauveine, 398 Meldola’s Blue, 372 Metamine Blue B & G [Z.], 372 Metanil Orange I & II [7.], 76* » Yellow [0.] [B.] [A.], 76 » Yellow 8 [0.], 76* Metaphenylene Blue B [C.], 401 Methyl Blue [C.], 325 » MBI for cotton [0.], 325 Methyldiphenylamine Blue [J/.], 330 Methylene Blue B & B G [B.], 882 an » 3B B in powder extra [B.] [17.] [A.], 382 Fs » B Bin powder extra D [4] [A.], 382 cp Gray [M.], 429 s Green extra yellowish conc. [i], 382* » Violet [D.Z.], 396 Methyl EHosine [A.], 349 3 » ([Mo.] [L], 347 , Green [By.], 311 gm (By) 805 » Orange, 74 » Violet B [B.] [By.] [A.] [C] M.), 303 0B, B04 » 6 Bextra [A.][C.] [27.], 307 » Water Blue [B.], 325 Mikado Brown B G M [Z.], 16 » Orange G to 4 R[ZL.], 17 » Yellow [Z.], 17 Milling Yellow [D.], 97 Mimosa [G. ], 100 Murexide, 428 Muscarine [D.H.], 374 Myrtle Green, 254 NAPHTHALENE RED, 397 5 Rose, 397 Fs Scarlet, 397 Naphthazarine 8, 263 Naphthion Red, 36 Naphthocyanine [ #. P.], 192 Naphthol Black 6 B[C.], 142 53 Blue Black [C.], 251 Green B [C.], 258 Orange [A.], 72 “e Yellow, 8 D LO ” » RS [By I 11 » S[Bh1 N aphthorubine [By.], 63 Naphthylamine Black D [C.], 141 Brown, 83 Naphthyl Blue [A.], 451 Naphthylene Blue R in crystals [By.], 372 5 Red [B.], 159 Narceine [D. H/.], 111 Neutral Blue [C.], 389 » Red [C.] [D.Z.], 388 , Violet [C.] [D.H.], 387 New Blue [C.] [By.], 372 New Coccine [A.], 88. ” ” R [A.], 64 ,, Fast Green 3 B [/.], 287 » Gray [By.], 429 5 Green [By.], 285 », Magenta [Jf], 300* », Methylene Blue G G [C.], 378 Hy 5 » N([C.], 385 5 Pink, 352 » Red [ZL], 438 New Red L [K.], 129 5, Victoria Green, 286 . » _ [B], 285 4 Yellow [By.] 75 oe eee (gear) 107 Lb} ” [B. K. ], 3 ” BLK} 20 Nicholson Blue [B.8.S.], 327 Night Blue [B.] [Z.], 297 » Green, 306 Nigrisine [P.], 429 Nigrosine soluble [A.] [B.], 403 3 spirit soluble [A.] [B.], 402 Nile Blue Fs [B.] [By.], 375 » » 2B[B], 376 Non-mordant Cotton Blue [B.S.S.], 329 OpaL BuuE [B.S.S.] [C.], 826 » _ [C], 828 Orange I, 72 3 11, 73 © Ill, 32 sy AMOI ARIB 7! G (CL, 27 » Brilliant [AL], 26 » Gold [By.], 73 Red I, 94 Orcelline No. "4, 84 Orchil Red A [B. 426 » Substitute G [A.], 37 WV [4.) [22,36 y 5 3 VN [P.][A.], 38 Fe extra [C.], 39 Oriol Yellow [G.], 101 Orseilline B B [By.], 132 Oxyphenine [CZ. Co.], 426 ” ” PALATINE ORANGE, 7 si Red [B.], 66 - Scarlet [B.], 48 Para-fuchsine, 299 Paraphenylene Blue R [D.], 404 a Violet [D.], 408 Parasulphurine § [B.4.], 171 Paris Green, 305 ” ” 293” 5, Violet, 303 On OU Patent Blue superfine, extra, B 294 Pee Ushio Pelican Blue, 402 Perkin’s Violet, 398 Persian Yellow [G.], 110 Persulphocyanogen Yellow, 427 Phenameine, 398 Phenamine, 398 Phenetol Red, 53 Phenicine, 432 Phénicienne, 432 Phenol Phthaleme, 340 Phenosafranine, 392 Phenyl Brown, 432 N [AL], Phenylene Brown, 149 Philadelphia Yellow G [A.], 421 Phloxine, 352 Be [Af], 355 As P [B.J, 352 » TA[Mo.], 355 Phosphine [B.S.S.], 421 Picric Acid, 1 Pigment Brown [B.], 60 Pink, 395 Pittakal, 338 Poeonine [G.M.], 337 Polychromine [G.], 425 ¥ B[G.], 163 Pomona Green, 306 Ponceau, 800* x B [MM], 129 5 G[C.], 49 % 2 G [A.] [B.] [AL], 28 Daerwanrwwnr ke by bd bd bd od bo HWW 3 Lee | eras | tea fr = hs i) co a 8 extra [4.], 130 i SS extra [A.], 118 as Brilliant 4 R [By.], 95 end Orient, 351 Primrose, 8 es a Valcool, 348 Es 9. LOA] 347 ‘ soluble [D.H.], 350 Primula, 309 Primuline [B.S.S.], 425 Printing Blue [A.], 402 Propiolic Acid [B.] [17.], 409 Prune, pure [K.S.], 369 Pure Scarlet [B.S.S.], 334 Purpurine, 398 ” [B.] [By.], 268 Pyoktanine, 303 Pyronine B [Z.], 283 4 G [Z.], 282 Pyrosine B [Mo.], 350 J [Mo.], 351 # R [4], 351* Pyrotine RRO [D.], 96 QUINOLINE BLUE [G.], 414 7 Red [A.], 415 +3 Yellow [A.] [B.] [By.], 418 spirit soluble [A.] [B.] [By.], 417 » water soluble, 418 Quinophthalone, 417 ” ” RAURACIENNE, 84 Red B [B.], 43 », Coralline, 337 » Deep [Cz.], 59 » Violet, 4R8 [B.], 302 5 R extra [B.], 309 PA » ORS[B.], 316 Regina Purple [B.S.S.], 317 je Violet wold spirit soluble [A.], 318 water soluble [A.], 319 Resorcin Blue [X.S.], 380 % Brown [A.], 146 * Yellow [A.], 71 Rhodamine B [B.] [JZ], 358 i S [By.], 359 ” ” ” ” ' Rhodamine S [B.] [By.], 360 Roccelline [D.H.], 84 Rosalan [P.], 398 Rosanaphthylamine, 397 Rosazurine B [By.], 218 a G [By.], 217 Rose B a Veau [J/.], 850 » J BaValcool, 348 » Bengal B[Z.], 357 5 » NIC} S54 . Bengale [B.], 354 » [BJ [C], 357 Roseine [B.S.S.], 388 Rosinduline B B & GG [K.], 407 Rosolic Acid, 385. Rosophenoline, 337* Rotheine, 482 Rouge de Naples, 428 », Frangais, 73* Roxamine, 443 Rubeosine, 345 Rubianite, 300 Rubidine, 84 Rubine, 308 ye Pet Soul Rufigallol [B.], 280 Russian Green [Z.], 254 SAFRANINE, 395 B, extra [B.], 392 Fe Extra G [A.], 895 S[C.], 395 a T [B.], 895 Safranisol LA.], 394 Saffron Substitute, 2 Saffrosine [/.] [B.S.S.], 349 Salicyl Orange, 5 » Yellow A, 4 Salmon Pink, 346* » Red [B.], 157 Scarlet 3 B[By.], 128 ee ey A) 3 (GRA as » J,dd,& V [Mo.], 849 » BR LBA AT 55 | O90 » Brilliant [C.], 88 » Double [K.], 127 Brilliant G [A.], 94 be » » 8R [By], 95 io » extra S$ [A.J], 95 » for Cotton, 30* Serge Blue 328 Sloeline [B.S.S.], 402 » RS&BS[BSS], 403 Solferino, 300 Soluble Blue [B.S.S.], 328 8B&10 B[B.S.S.], 324 33 » XG [BSAS1, 329 » & LLB SS. 325 Spirit Blue Bi SoS.) Bale son ee 326 ” ” 39 ” » Hosine, 348 » 9» [BI], 347 » Lellow, 19 St. Denis Red [P.] [A.], 155 Stilbene Red [A.], 161 » G[A.], 161* Styrogallol, 261 Sudan, G [A.], 22 » Brown [A.], 60 4 Red, 397 Sulphanil Yellow, 171 Sulphine [B.], 425 Sulphone Azurine [By.], 201 Sun Yellow, 9 ” ” 15 TARTRAZINE [7.][B.], 18 Terra Cotta F [G.], 106 7, RIG | 109 Thiazol Yellow [By.], 99 Thiocarmine R [C.], 386 Thiochromogen [D.], 425 Thioflavine S [C.], 424 3 T [C.], 423 Thionine, 381 os Blue GO extra [A/.] [A.], 383 Thiorubine [P.], 68 Toluidine Blue [B.] [AL] 384 Toluylene Blue [0.], 406 is Brown [0.], 151 3 Orange G [0.], 215 ” » R[O.], 216 4 Red, 388 Tropoeoline D, 74 4 G [C.], 76 R 5 000 No. 1, 72 x 000 No. 2, 78 r OOOO, 24 Turmerine [B.S.S.], 99 Tyraline, 398 [A] r 205 | | Uranine [B.] [4.] [Z.] [1/.] [BSS], 342 Uscbe’s Green, 416 VERT-DE-Pants, 293* » 5, Methylaniline, 305 », Diamant [Jo.], 285 », Htincelle [dfo.], 305 » Lumiére, 305 6 3 306 Vesuvine, 149 Victoria Black [By.], 445 % Blue B [B.] [Z.], 296 ” » 4R[B.] [ZL], 298 ,» Green 3 B[B.], 287 a Orange, 2 » Red, 208* 5 Yellow, 2 Violamine R [JL], 449 ; B [1/.], 450 Violaniline, 402 Violeine, 398 Violet 5 B [By.], 307 » 6B [By], 307 » R[Mo.], 309 » KR [Mo], 309 » OR[By.], 309 » Black [B.], 154 » de-Methylaniline, 303 , Impérial, rouge, 317 THE END Printed by R. & R. Ciark, Edinburgh. Violet phenylique, 317 » solide [D.H.], 368 Viridine, 293 Water Buus [B.] [By.], 328 % » 6B extra [A.], 328 5, soluble Eosine [MZ], 346 White Indophenol, 366 Wool Black [A.] [B.], 131 » Green § [/.] [B.], 441 » scarlet R [Sch.], 46 » Yellow [B.], 31 XYLIDINE Rep, 50 - Scarlet, 50 YELLOW T [/.], 71 » WI[By.], 21 - Brilliant [Sch.], 11 3 Brilliant $ [B.], 77 9 Coralline, 336 2 fast-to-soap, 98 Gold [ By.], 71 ~ Indian [By.], 108 3 New [By.], 75 [B.K.], 3 ” ” L [K.], 20 a Persian [G‘.], 110 ” ” ZINALINE, 6 MESSRS. MACMILLAN & CO’S BOOKS FOR CHEMICAL STUDENTS. ESSAYS IN HISTORICAL CHEMISTRY. By T. E. Tuorpe, F.R.S., Professor of Chemistry in the Royal College of Science, South Kensington, London. Crown 8vo. 8s. 6d. net. HISTORY OF CHEMISTRY FROM THE EARLIEST TIMES TO THE PRESENT DAY. By Ernst von Meyer, Ph.D. Translated by GkEorcE McGowan, Ph.D. 8vo. 14s. net. EXPERIMENTAL PROOFS OF CHEMICAL THEORY FOR BEGINNERS. 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