TRIPHENYL METHANE COMPOUNDS 
 

 X ^ 
 
 
 
 ,^i'*' ■ 'T"'^ 
 
 
UNIVERSITY OF ILLINOIS 
 
 
 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY 
 
 QMN__MApFQRB_0^^^ 
 
 ENTITLED 
 
 IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE 
 DEGREE OF a_e_l P_r _ _qf _ _S c_i p n ^ e _ _iij_ _C he_nLis t_rj_ 
 
 HEAD OF DEPARTMENT OF 
 
Digitized by the Internet Archive 
 
 in 2016 
 
 https://archive.org/details/triphenylmethaneOOgran 
 
lEDEX 
 
 I. 
 
 II. 
 
 III. 
 
 IV. 
 
 Y. 
 
 VI. 
 
 Introduction 
 
 Historical 
 
 Theoretical Consideration 
 
 Experimental 
 
 SUiTunary 
 
 Bibliography 
 
 1 
 
 2 
 
 3 
 
 17 
 
 26 
 
 27 
 
 OBG/SW 
 
ACZUOWLEDGiiMSHT 
 
 I wish to express my sincere gratitude 
 and appreciation to Dr. .Eoger Adams for the 
 assistance and inspiration given me during 
 the course of these experiments. 
 
fl) 
 
 I. 
 
 INTEODUCTIOH 
 
 In spite of the fact that dyes of the triphenyl methane 
 series are among those first hnov/n and at present have a very 
 extended use, methods for their production are unsatisfactory, 
 giving low yields and often their structure is misunderstood 
 or even unhnown. Hence, any work which will improve yields 
 and throw light on the structure of these compounds v/ill he 
 welcomed hy both the theoretical chemist and the dye plant 
 enterpreneur . 
 
 The following i/vork was undertaken with this object in 
 view, with special emphasis on improvements in methods of pro- 
 ducing Spirit Blue dyes. Direct synthesis was attempted, thus 
 eliminating the possibility of the many side reactions so detri- 
 mental in the common process which is the phenylation of fuchsine. 
 

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( 2 ) 
 
 II. 
 
 HISTORICAL 
 
 The first known artificial dyes vt^ere those of the 
 triphenyl methane type and v/ere discovered at approximate- 
 ly the same time, 1856-58 hy chemists of England, France, 
 and Germany. Hathanson is given priority, w^hile f erkins , 
 Hoffman, Eoguencount and Tort follow in line. 
 
 Since then great Strides have taken place in their 
 manufacture, hut due to the fact that owners keep their 
 processes as secret as possible very little information has 
 been published. 
 
 Girard and de Laire are accredited with the discovery 
 of triphenyl rosaniline in 1862. 
 
 The method upon v/hich the following work is based was 
 discovered in 189E by chemists of Geigy & Company, Basel, 
 Switzerland. A patent of that year describes the process. 
 Since then, no work has been published on it. 
 

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III. 
 
 TT) 
 
 TEEOEEIICAL COESIEERA-TIOES 
 
 Spirit Blue is described in the literature as tripheny- 
 lated rosaniline, 
 
 XZ3'*^<IZ> 
 
 \ — >«-< > 
 
 and Alkali Blue, Soluble Blue, and V/ater Blue as the 
 mono, di, and trisulphonic acids respecively. 'The sulphonic 
 
 group goes para to the amino group. Liore or less is to be 
 
 V 
 
 found on methods of their preparation, but this is practically 
 all that may be found on the struct of these compounds. 
 
 The common method of making Spirit Blue and its de- 
 rivatives is to first prepare Buchsine by heating a mixture 
 of aniline, aniline hydrochloride, para toluidine, nitrobenzene, 
 zinc chloride, and iron oxide at 160 degrees for twelve hours, 
 llie resulting low yields are readily understood when the complex- 
 ity of this mixture is considered. Birst toluene is oxidized by 
 the nitrobenzene to p-amino benzaldehyde. This in turn condenses 
 with two mols of aniline to give the leuco base. 
 
Upon further oxidation by the nitrobenzene this yields 
 
 vvhich inimediately forms luchsine with the hydrochloric acid 
 present in the aniline hydrochloride. 
 
 It is highly improbable that all these reactions could 
 take place simaltaneously in one mixture and give the best re- 
 sults. The importance of correct temperatures for various re- 
 actions is only too well known. Furthermore the presence or 
 absence of acid, water, or catalyzer may promote one reaction 
 and retard another, h'ith all these in one mixture we have no 
 method of control, which w/ould make them function properly for 
 each reaction. 
 
 Perhaps even more important than incomplete reactions 
 are the formation of many undesirable products, so called side 
 reaction products. In fact these make up the greater part of 
 the product and represent at least 70^ loss on the wei^.t of the 
 materials used. 
 
 The possible side reactions are too many to enumerate. 
 It is sufficient to say that the finished Fuchsine melt contains 
 only 12 to 15^ pure color. 
 
 A typical analysis is: 
 
 Pure color 
 
 13% 
 
 Aniline oil 
 
 7^ 
 
 Kesidue 
 
 65% 
 
 Moisture 
 
 26^ 
 
( 5 ) 
 
 The formation of Rosaniline is easily accomplished hy add- 
 ing sodium hydroxide solution to a solution of Ruchsine. The 
 reaction proceeds almost quantitatively. 
 
 Information on the chemistry of phenylation is entirely 
 lacking, ^he literature merely states that v/hen a mixture of 
 Rosaniline and aniline are heated together v/ith the proper 
 catalyst, triphenyl rosaniline is fonned. If this were the 
 case, only one shade of blue could he obtained v/hile in 
 practice, shades ranging from a very reddish blue to a green- 
 ish blue are readily obtained by proper control of the re- 
 action. 
 
 The various shades are merely different degrees of 
 phenylation. Thus 
 
 is a very red shade blue. 
 
 H 
 
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 H 
 
 
 a pure blue and 
 

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( 6 ) 
 
 a very green shade blue. Actually, the product is a mixture 
 of the above and may be separated by their difference of 
 solubilities in aniline hydrochloride. Even samples of 
 the greenest shade blues are found to contain a very small 
 amount of the monophenylated product. 
 
 Yields are fairly satisfactory, being 70 to 80^ of 
 theoretical. It is cut down by aniline reacting v/ith 
 itself to form diphenylomine and also hosaniline mole- 
 cules condensing with themselves. 
 
 The greatest disadvantage in this process is that the 
 shade cannot be controlled. It is impossible to run dipli 
 cate melts v/hich give identical shades. Furthermore, the 
 greenest possible shade is not obtainable by this method, 
 for the reason that the Eosaniline molecules will not re- 
 act completely v/ith aniline to form the triphenylated 
 product. Some mono and diphenylated rosaniline is always 
 present in the finished melt. Then too, the longer the 
 reaction is carried out, the lower will be the and 
 
 as the dye users demand a green shade, considerable loss 
 
 occurs in prolonging the phenylation in order to obtain 
 these green shades. 
 
( 7 ) 
 
 In view of these facts a synthesis which i/vould give pure 
 compounds would insure uniform shades and improve yields. 
 
 The sulphonation of Spirit Blue goes easily, inasmuch 
 as 95^ sulphuric acid is sufficiently strong to give any 
 degree of sulphonation, vis. from a mono to a trisulphonated 
 product. However, greatest care in temperature control and 
 length of time must he exercised. Strict trade specifications 
 require that the solubility in sulphuric acid solution be 
 exact for the respective dyes Alkali, Soluble and Water Blues. 
 Careful chemical control is necessary and even then many 
 batches are oversulphonated. 
 
 Different shades require different lengths of time for 
 sulphonation, also different proportions of acid to Spirit 
 Blue. Prolonged sulphonation or too strong acid weakens 
 the resulting dye. 
 
 Thus it is seen that the many factors entering into 
 sulphonation make the present method unsatisfactory. 
 
 In view of the fact that yields on Puchsine are very 
 low and accurate control of phenylation and sulphonation 
 are impossible, the present method of production of Spirit 
 Blue and its derivatives is very unsatisfactory. 
 
 The possibilities of the new process have never been 
 

 
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The reactions taJce place in two steps. Heaction one 
 is the first step and the remainder of the reactions the 
 second step. 
 
 The resulting product has a much greener shade than 
 any product obtained from the old process and, as would 
 he expected, is very soluble. 
 
 The conditions for this reaction are ideal. The 
 possibilities of side reactions are very small. The sul- 
 phonic group makes the para hydrogen of the diphenylamine 
 very reactive enabling the condensation to proceed very 
 easily, ho condensation agent is required. In fact, the 
 presence of more than a very small amount of hydrochloric 
 or sulphuric acids yields a hard insoluble product. 
 
 Again in the second step, the possibility of side 
 reactions is neglegible. Thus in the reaction 
 
 the third molecule of diphenylamine monosulphonic acid must 
 go in the right place or not at all. 
 
 The most desired dye of the Spirit Blue series is Allcali 
 Blue which contains only one sulphonic acid group. The red 
 

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 shade could be obtained by oxidizing a diphenylamine mono- 
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 and the green shade from 
 
 ^ cy^^~<z>so,H 
 
 The intermediate blue shade could be made by mixing 
 the red and green shades in the proper proportion. 
 
 In order to produce the green shade by the above method, 
 the present low yield obtained in the preparation of 
 
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 would have to be raised 
 

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For Soluble Blue dyes 
 
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 v.’ould give a blue shade and 
 
 ^ /<!> 
 
 ^ 0^-0 
 
 a green shade. 
 
 The procedure for mahing Water Blue, the trisulphonated 
 compound, has already been given above, i.Iany other shades 
 could be obtained by using dimethylaniline in various com- 
 binations. 
 
 Certain facts brought out in experiments with these 
 dyes have demonstrated that much is to be learned about 
 their structure. The colloidal nature of these compounds 
 is shown in certain tests which the manufacturers make. 
 
 The specifications of Alkali Blue for lithographic inks 
 require that v/hen two grams of the sample is dissolved 
 in 100 cc. of water, it shall be precipitated with 1.3 cc. 
 of ten times diluted 93% sulphuric acid. As the acid is 
 

T.^rr^TT— ■; 
 
 added., an extremely fine precipitate first appears, then as 
 the end point is reached a heavy precipitate suddenly appears. 
 If the solution is made up to 200 cc. instead of 100 cc. , just 
 twice as much acid is required to cause precipitation, showing 
 that the concentration of the acid only is the determining 
 factor. Soluble Blue (the disulphonic acid compound) requires 
 about 17 cc. of the standard acid to cause precipitation. 
 
 Water Blue cannot be precipitated with any amount of acid. 
 
 A study of the colloidal nature of the various sulphonated 
 blues should prove a valuable contribution to this branch 
 of chemistry. 
 
 Varying conditions in the last steps of Akali Blue manu- 
 facture produce dyes which require more or less of the 
 standard acid for their precipitation. 
 
 Sodium hydroxide is added to the free acid of Alhali 
 Blue to form a soluble salt. If just sufficient alhali is 
 added to render it soluble, 2.5 to S.O cc. of the standard 
 acid is required for precipitation. If now more alkali is 
 added so that the finished dye v/ill contain approximately 
 tw'ice as much sodium, it v/ill be precipitated with less 
 than half the amount of acid than that required for the same 
 dye containing less alkali. 
 
 The rate and temperature at 'which the Alkali Blue solution 
 is evaporated also cause a marked change in the precipitation 
 point. It would seem from the above that Alkali Blue possesses 
 
( 12 ) 
 
 two structures* The one usually given is 
 
 
 I'rom certain experimental facts and also the well estab- 
 lished structure of the simpler triphenylme thane dyes it 
 seems reasonable to believe that Alkali Blue possesses 
 the following structure: 
 
 The structure for Spirit Blue from which Alkali Blue is 
 derived is well established* 
 
 The chlorine is firmly attached for it can not be split 
 off even with boiling sodium hydroxide* 
 
 When concentrated sulphuric acid is added to this com- 
 pound, hydrochloric acid is iiomediately given off* It seems 
 logical to believe that the hydrochloric acid is merely dis- 
 placed and that the sulphuric acid goes on in it place to give 
 
 
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 Upon continued action of the sulphuric acid, sul- 
 phonation takes place. The melt is then poured into 
 water and vi/ashed acid free, and sodium hydroxide added 
 until material is completely dissolved. If just enough 
 sodium hydroxide is added, the product is completely 
 soluble and is a deep blue color. It must possess the 
 quinoid structure because it is colored. This is easily 
 explained if we assume the hydrogen of the free sulphonic 
 acid is replaced by the sodium to give 
 
 If now more sodium hydroxide is added, the solution 
 becomes weaker and v;hen approximately twice as much sodium 
 hydroxide is added, the solution becomes colorless. The 
 second addition of alkali removes the sulphuric acid from 
 the nitrogen to give the base thusly. 
 
 c 
 
 0^-0 
 
 ^ H- _ 
 
 \ 
 
 ■O N 
 
fl5) 
 
 just sodium hydroxide removes the hydrochloric acid from 
 Fuchs ine and gives the hase. 
 
 HO - C 
 
 O it/, 
 
 O Y 
 
 If now sulphuric acid is added, a deep "blue precipitate 
 is formed. This is the same compound that was originally 
 formed in the melt* 
 
 There is no reason to "believe that these phenylated 
 rosanilines should react different than the corresponding 
 alkylated compounds. Thus 
 
 
 N 
 
 ■On 
 
 0*-/v 
 
 \ 
 
 ' cfYj 
 
 ■ C.f/j 
 
 - H 
 
 ■ H 
 Cl 
 
(16) 
 
 reacts Vvith sodium hydroxide to give 
 
 HO^C 
 
 <3 
 
 a colorless compound and when this "base is treated with 
 hydrochloric or sulphuric acid the original color is re- 
 stored. 
 
 The behavior of Alkali Bluei, as well as the general 
 reactions for this type of compounds indicate that 
 
 
 V ^ 
 
 <3 
 
 -<3 A' ^ <3 
 
 is its true formula. To prove conclusively, an analysis 
 would have to made on the free acid of Alkali Blue. 
 
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IV, 
 
 fl7) 
 
 Condensation of I-iphenylamine. 
 
 Experiment I. 
 
 50 g. of diphenylamine was dissolved in 100 cc« of 
 ethyl alcohol in a round bottom flask and 11.1 g. of 40^ 
 formaldehyde added. The temperature was raised to 60 de- 
 grees and 2.5 cc. of 20^ hydrochloric acid added. Vigor- 
 our reaction took place immediately. Flame v;as removed 
 but temperature rose to 82 degrees, then gradually sank. 
 
 At the end of 15 minutes no odor of formaldehyde v/as pre- 
 sent and Fuchs ine aldehyde reagent gave negative test. A 
 heavy viscous brown liquid soon settled on the bottom, 
 v;hile the upper layer remained turbulent. The contents 
 were allov;ed to stand two days, during which time the brown 
 layer became hard. This solid v;as extracted with three 100 cc. 
 portions of ethyl alcohol. 27 g. of diphenylamine w^as re- 
 covered by precipitating it from the alcohol w^ith water. 
 
 The yield of diphenyldiamino diphenylme thane was 7.5 a 
 
 = 15 ^. 
 
 M. P. 79 to 90 degrees. It did not give a sharp melting 
 point. 
 
 The material was dissolved in 50^ sulphuric acid and the 
 solution poured into water. The resulting precipitate was 
 dried. 
 
 Weight 7g. 
 
 M. 1. 95 to 100 degrees. 
 
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Experiment II. 
 
 mf 
 
 This experiment was a duplicate of experiment one up to 
 the point of extraction. In this experiment the hrown solid 
 was extracted with three 100 cc. portion of ether. 
 
 Recovered Diphenylamine S3 g. 
 
 Yield 8 g. 
 
 M- P. 145 to 150. 
 
 The diphenyldiaminodiphenylmethane was recrystalized 
 from benzene. 
 
 M. P. 155 to 159. 
 
 Oxidation of diphenyldiaminodiphenylmethane. 
 
 Experiment III. 
 
 A saturated solution containing 10 g. of copper sulphate 
 was poured over 40 g. of sodium chloride and the vdiole dried. 
 6 g. of diphenyldiamino diphenyl methane was dissolved in 3 g. 
 of phenol and 6 g. of diphenylamine and poured over the above 
 salt, heated at 65 to 70 degrees for 24 hours. A very good 
 blue color resulted, but no means of purification could be 
 found. 
 
 Sulphonation of Diphenylamine. 
 
 Experiment IV. 
 
 6 mols of acid to 5 of diphenylamine. 
 
 85 g. of diphenylamine was melted in an evaporating dish 
 
(19 
 
 dish and 54 cc. of 95$^ sulphuric acid added. The mass became 
 very viscous and hard to stir and soon turned black after the 
 temperature had been raised to 160 degrees. 
 
 Considerable sulphur dioxide was given off. After one 
 hour heating at 160 degrees the mixture Vs/as found to be in- 
 soluble in alkali and alcohol. The diphenylamine had been 
 oxidized. 
 
 54 g. of diphenylamine was heated to lEO degrees in a 
 400 cc. beaker and 6 cc. of sulphuric acid (95fo) added with 
 stirring. 
 
 The color of the mass Vvas light green and it soon became 
 very viscous. Temperature was raised to 160 degrees which 
 caused effervescence to take place. Melt was held at 150 to 
 160 degrees for 40 minutes and then poured into EOO cc. of 
 toiling W'ater , neutralized v;ith lime and vhile solution ?/as 
 hot it 7v'as filtered. The residue was extracted and found to 
 contain 14 g. of diphenylamine. 
 
 The filtrate was allowed to cool and the crystals of 
 calcium diphenylamine monosulphonate filtered off. It was re- 
 crystalized from hot water and some diphenylajuine separated on 
 the filterpaper. 
 
 Experiment V. 
 
 E mols diphenylamine 1 mol acid 
 
 Yield 11.5 g of 
 Equal to 
 
Experiment VI. 
 
 Experiment five was repeated. Eeaction proceeded the 
 same as before. 
 
 Yield 9.7 g. 
 
 Equal to E9.0/^. 
 
 Experiment VII. 
 
 1 mol of diphenylamine to 1 of acid. 
 
 85 g. of diphenylamine v/as heated in an evaporating 
 dish to 120 degrees and 28 cc. of sulphuric acid (95^) 
 slowly added. At first the liquid solidified but upon 
 the addition of the remainder of the acid it again became 
 liquid. Temperature was raised to 160 degrees and held. 
 Almost immediately sulphur dioxide v^as given off and the 
 melt turned to a hard black mass. It v/as insoluble in 
 sodium hydroxide. 
 
 Ibcperiment VIII. 
 
 1 mol diphenylamine to 1 mol of 50^ sulphuric acid. 
 
 From this experiment on, a 400 cc. flask provided 
 with an ajitator was used and an oil bath. 
 
 42 g. of diphenylamine was melted in a flask and 28 cc. 
 of 50^ sulphuric acid added. Temperature raised to 160 
 degrees; held there for 2 hours and then raised to 180 de- 
 grees. The v/ater gradually evaporated out and the sulphon- 
 ation then proceeded as in experiment seven. Sulphur di- 
 

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( 21 ) 
 
 oxide was given off. The mass v/as boiled up with sodium hy- 
 droxide solution. A green powder resulted which had a M.P. 
 over 250 degrees. 
 
 Experiment IX. 
 
 1 mol diphenylamine to 1 mol of 75^b sulphuric acid. 
 
 4S g. of diphenylamine was melted and 14 cc. of acid 
 plus 4.7 cc. of water added. The reaction and results were 
 the same as in experiment eight. 
 
 Experiment X. 
 
 2 mols diphenylamine to 1 of acid. 
 
 85 g. of diphenylamine ¥/as melted in the flask and 28 cc. 
 of sulphuric acid slowly added. Considerable frothing took 
 place. Temperature was raised to 160 to 170 degrees and held 
 there for six hours. Melt was poured into hot v/ater and 
 neutralized with lime. Solution allo?;ed to partially cool to 
 45 degrees and filtered. Upon cooling the calcium diphenylamine 
 monosulphonate crystalized out. 
 
 Yield 52 g. equal to 46.7^ theoretical. 
 
 Experiment Jx.X * 
 
 Experiment ten v/as repeated holding the temperature be- 
 tween 180 and 190 degrees. After about four hours heating the 
 temperature accidentally ro3e to 235 to 240 degrees. Sulphur 
 dioxide was evolved and the melt turned hard and black the 
 same as when too large a proportion of acid v/as used. 
 
( 22 ) 
 
 Experiment ill. 
 
 Experiment ten v/as repeated and the temperature held 
 at 180 to 190 degrees for 16 hours. At the end the melt 
 had a very light pink color. It was poured into hot v/ater 
 limed and the diphenylamine and excess lime filtered off hy 
 partial cooling. 
 
 Yield of diphenylamine monsulphonate 57 g. equal to 56.2^ 
 
 Recovered diphenylamine 54.2 g. equal to 42^. 
 
 Experiment XIII. 
 
 Experiment twelve was repeated but this time the sulph- 
 onation melt was poured into hot water and sodium carbonate 
 added till neutral. Solution was cooled and the unreacted 
 diphenylamine filtered off, 58 g. equal to 44.7 recovered. 
 
 The sodium siphenylamine monosulphonate was evaporated 
 dom to dryness and used in a condensation experiment. 
 
 Yield 45 g. 
 
 Condensation of Calcium diphfmylamine monosulphonate. 
 
 Experiment XI7. 
 
 20 g. of the calcium salt was dissolved in 100 cc. of 
 water and 5 cc. of 40^ formaldehyde added. Solution v/as 
 heated on water bath till dryness (4 hours). 
 
 Residue was a grey soluble solid. 
 
 Yield 19 g. equal to 95^. 
 
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I^periment XV. 
 
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 This experiment was run the same as XIV. except that 
 1 cc. of 20fo hydrochloric acid was added the solution to 
 catalyze the reaction. As evaporation took place the solu- 
 tion hecame brown and viscous. At the end the residue was 
 hard and dark brovm and insoluble in water. 
 
 Various methods of oxidation were attempted but no color 
 could be obtained. The hydrochloric acid proved very detri- 
 mental to the condensation. 
 
 Experiment XVI. 
 
 This Vifas run the same as experiment XIV. except that a 
 few drops of sodium hydroxide was added to mal:e it distinctly 
 alkaline. The residue was a very light grey and water soluble. 
 That it was only a partial condensation was shown vh en it was 
 oxidized to the color. 
 
 Yield 19.5 g. equal to 95.6/'o 
 
 Oxidation to the Dye. 
 
 Experiment XVII. 
 
 10 g. of the condensation product v;as dissolved in 50 cc. 
 of water. 5 cc. of concentrated sulphuric acid and 5 g. of 
 calcium diphenylamine monosulphonate added, then a solution 
 containing 10 g. of potassium chlorate. The solution first 
 became blue and then very quickly changed to a black. The 
 oxidation could not be controlled. 
 
(S4) 
 
 Experiment VIII. 
 
 Carried out the same as experiment iVII. hut potassium 
 dichromate wss used in place of the potassium chlorate. 
 
 Results v/ere the same as in proceeding experiment. Lower- 
 ing the amount of acid and oxidizing agent did not change the 
 results* 
 
 ExperimentZIX. 
 
 10 g* of the condensation product was dissolved in 60 cc. 
 of water and 5 g. of calcium diphenylamine mono sulphonate added, 
 then 5 cc. of hydrochloric acid. The solution was cooled and 
 15 g. of powdered lead peroxide slowly added with agitation. 
 Solution first turned light green then became darker and darker 
 till a deep blue color was reached. Ammonium carbonated was 
 added the soluble salt of the dye filtered from the lead sludge. 
 Resulting dye was a very green shade blue and dyed silk and wool 
 a very good shade. 
 
 Experiment XX. 
 
 Run the same as experiment XIX. except that EO cc. of glacial 
 acetric acid was used in place of the hydrochloric. The solution 
 turned brown and then a very dark brown, as a final product. 
 Smaller amounts of acetic acid gave practically the same results. 
 
 Experiment XI. 
 
 Run the same as experiment XIX. except 5 cc. of concentrated 
 sulphuric acid was used in place of the hydrochloric acid. The 
 reaction proceeded much slower than when hydrochloric acid v;as 
 used. Ro blue color developed for five bourse. Reaction was 
 
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 Two mols of diphenyl amine to one of sulphuric acid v.as 
 found to he the best ratio for the production of diphenylamine 
 monosulphonic acid. TempeKture should he 170 to 180 degrees. 
 
 Condensation of calcium diphenylamine monosulphorate with 
 formaldehyde tahes place best in a neutral solution and with an 
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 The most satisfactory oxidizing agent was found to he lead 
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Eeferences : 
 
 ( 27 ) 
 
 Diphenylaraine monosulphonic acid 
 
 V.'inthers Volume I Page 571 Patent Eo. 12,745 
 
 Berichte " 6. " 1615 
 
 Diphenyldiaminodiphenylme thane 
 
 V/inthers Volume II " 48 " " 58,072 
 
 Water Blue 
 
 Winthers "II " 149 " " 75,092 
 
 Preparation para Puchsine 
 
 Priedlander Volume III " 112 
 
 (1890-94) 
 
 Biaminodiphenyl Methane 
 
 Priedlander Volume III. " 55 
 
 Anhydro f ormaldehydeanilin 
 
 Berichte Volume XVIII " 5509