SjfnTh&si^ Of (^uint jtourart , / ^ 4 « SYNTHESIS OF QUINIZARIN BY RALPH WALDO FOOLER THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE IN CHEMISTRY COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1921 Digitized by the Internet Archive in 2016 https://archive.org/details/synthesisofquiniOOfogl UNIVERSITY OF ILLINOIS ) 31 \ 192I 00 01 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY ML£H__WALD 0_ _ PO GLEB. ENTITLED IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF BaciieXQr__or__E.aJLeiiiie._iii_iloeials.trY Instructor in Charge Approved HEAD OF DEPARTMENT OF S9 0T \Wi ' " w^i j(tV\ V» *“« (A «»!^ 1 ■\,J^ ^ ,■ ^* ';%(» ' -'‘f* • fs B <-«Ti- ' « '>'>» _ * "■, IT' ' «v*ii'«;i; ■>* * ■ — 1 N * i • ^'= -St xJ" 4t ULJfek ■ ( , ■■■^■' A. ■■-■ .3- 'j. va V!Qi^av3iinv-: YKJi:*Kt^.u ^ , ’' lIS •' "WoDI' ^iBS V' ' >^1? :t m 1> r. esWiv:...,, i !( "' u - 1 - ’' ■ * — i ? ■■’ ^ " '. ' Mb . ■ * U - ■■' J ' 7-. ■ •* -s m iJf Jr -- !•-■ <» , Aj*" .»■* ■. '* . . :rHt iign stTVi-u/; •«'TKAn,?,iiir f' n Vi4 Y4<3T^OHW?«ft ^ ' - . ' ■; '(•,, 'V \ ’.T; : . iU .ii auftXn|iCvlo'-rvvI«>/^ii!L^ * ji , t I ' / I" U.^. f. ^ V : ■ ?.'« i ’ >•■. ,/»*-'V©«Hri -V 1 tIS *1 TABLS OF C01ITEBT3 Page IliTRCPUGTIOE 1 HISTORICAL PART E THEORETICAL P;^RT 12 EXPERIIIERT^L PART 13 SULIMARY AEL COECLUSIOE EO BIBLIOGRAPHY 21 ACMOWLEPGIvISilT r AGMOV/IEDGL'EUT The author, at this point, ?/ishes to express his appreciation of the help that Doctor Roger Adams has been, under v/hom this v/ork has been done. This problem selected by Doctor Adams has proven very profitable and interesting, and his attentive help has been of great assistance. » ' ^ -’'®wnii" K s»' V' ‘ wi ' '%* pfiip,, 5 !fj* ..'jOiaV-®^/ •. ■\)i’~r-v r , .-,- J- %4l ,■ ',<*• ►!f.ii r> '* .. - ' t; ^ . ‘. ^ :l IJj, «-?W > T<^ . . i . / -to ,^.« ■ fe;^*43Nit • ^-' •■» '‘•'okiiv * vi 1 '• ,^. ;. .-I ’•♦ •: .■•‘'>Jf / ■ ' ^'I^V 5 V-i' '-.‘a. • ?■ • _■ • f>' . t>4-tvJ aye .'! > ; . j 'A »> ^."vf . t. '. •V . ; Vj ■ 'V » ■ ;v- Wj • '00^1 .V /a ■' 5 -. ^1 i‘ , * -» •» , > '• . r** ■ ,-v 7^ - ^ vA ; ?'• o.;a.. ■ '< , ■' ■ •- - . . r . ->’A^ J.'^CGr . or *- ; A : t > s T.'.r , . 1 .' r , r '1 ^ . -•>'.; i ::? Tvr y i ' s *( V ' r <- : :’ i > & ■!1 -fi ro ' .'1 ’'-' , -i .-sT 9 ;; t , ^ ft ^' ■ I ’ i ' 7 * i^v ) W 3 Si .X T ' . i*i • » n / ^ * . • • .'4 i -i i - /' V r ~ " j! ** '■ - ..*' ' XT 2 - I-HSTOHIGAL PART Ciuinizarine . Tuinizarine is by no means a new compo'und. This compound was first obtained R. Grimm, in 1873, by condensing phthalic anhydride with q^uinol -OH However, only a small fractional yield of the theoretical yield was obtained. The following processes have been patented, (1) Prom anthraq^uinone — (a) a mixture of 10 parts of anthra- cuinone , 10 parts of crystallized boric acid, and 200 parts of sulfuric acid is heated. An energetic action sets in at 260-280 0. Sulfur dioxide is evolved, and the formation of q_uinizarin is complete in a short time. + 3 If the heating is continued, purpurin is formed. o H,8£>3 -f y 0 The complete formation of q^uinizarin is ascertained by spectroscopic test on a sample diluted with sulfuric acid . The mixture is pour- ed into water and the quinizarin filtered off. If necessary, it can be purified by dissolvii'.g it in allrali, and precipitating vdth acid . (b) Pourteen parts of sodium nitrite are added to 200 parts of cooled sulfuric acid and when all is dissolved , 10 parts of anthra- quinone and 10 parts of crystallized boric acid are added. The 1 F 3 - mixture is stirred and heated as q^uickly as possible to 280-230 . At 180-190 , the reaction takes place, T??hich is complete after heating for two to four hours at 220-230 . When cool, the mixture is poured into Vvater, the vhiole boiled to decompose the boric ester v/hioh is first formed, and the q.uinizarin is filtered off. Al- ternatively gaseous nitrous acid can be passed into a solution of 10 parts of anthraquinone and 10 parts of boric acid in 200 parts of sulfuric acid, and the v/hole is heated to 220-230 until the solutf (o) Ten parts of sodium nitrite are slovay added to 120 parts of sulfuric acid, followed by 7 parts of anthraquinone and 1.6 parts of mercuric sulfate, and the mixture is heated until at 180 , the mass is brownish red. The temperature must not be allowed to rise above tnis point. When cool, the mass is poured into water, the precipitate dissolved in sodium hydroxide solution and boiled for half an nour , v/nen the solution is filtered from any unchanged anthrac[uinone ano then acidified to obtain Q_uinizarin. ( 2 ) From er/throhydroxanthraq^uinone , (l-hydroxyanthraquinone ) Twenty parts ox sodium nitrite are dissolved in 600 parts of sulfuric acid, and 30 parts of boric acid and then 30 parts of erythrohydroxy- anthraquinone are added. The mixture is heated to 180-200 until a spectroscopic test shows no increase in the amount of quinizarin. xhe mass is cooled, diluted with v/ater, boiled, and the quinizarin filtered off. (3) li'rom phthalic anhydride and p-chlorophenol . Eighty parts of phthalic anhydride, 20 parts of Ix) ric acid and 23 parts of p- chlorophenol are mixed v/ith 400 parts of sulfuric acid, and the mixture is heated for three hours at 150 . The temperature is then raised to 180-200 and lept at this point until the amount of quinizarin no longer ire reuses. On cooling the mass is poured into twenty times its q^uantity of water, and the quinizarin is filtered off. It is purified hy extraction with a large quantity The yield is 70-80fo of the theoretical. Alternatively, a solution of 60 parts of p-chlorophenol in 200 parts of fuming sulfuric acid (containing 20^ of sulfur tri oxide) is heated to 130-140 until a sanq^le , when added to a 12^^ solution of salt, gives no precipitate, showing the formation of p-chlorophenoldisnAfuric acid. T v/o hundred parts of sulfuric acid, 40 parts of boric acid, and 80 parts of phthalic arihydride are now added and the mixture is heated as described above. After some time, dark blue crystals of the ester, *^14%^4*^^3^2^3 separate out. \lheu the quantity of this no longer increases, the mass is cooled, and the ester filtered on an asbestos filter, washed with sulfuric acid (60 Be'), and finally with ice water. On boiling it v/ith water or sodium carbonate solution, it is converted into quinizarin. (4) Erom purpin. To tv/enty parts of purpin and 7 parts of boric acid was added 30 parts of concentrated sulfuric acid, and this was stirred. ’.7hile stirring strongly, 5 parts of aluminium 5- powder was added, and the temperature kept belov/ 50 . Vifhen the solution turned golden, the mixture was poured into water, and filtered off, and dried. (5) From 1-4, diohloroanthraq,uinone . Forty parts of 1-4 dichloroanthraq_uinone was mixed with IOC parts of concentrated sulfuric acid (10^ 30g), and 5 parts of boric acid at 200 0, It was then poured into water and filtered. -d Mo ^6 ^ +T + H3BO3 ^ (6) From 1-4 chloroxyanthraquinone . Ten parts of 1-4 chloro- oxyanthraq^uinone was mixed vlth 50 parts of oleum (20^), and 50 parts of sulfuric acid of 66 Be'. Then 5 parts of boric acid was was e.on,^]et& added, and the temperature kept at 100 until formation of quinizariij)? This concludes the work w^hich has been carried out on the sjuithesis of ouinizarin up to this time. P-chloroxyanthraquinone . P-chloroxyanthraquinone , a derivative of anthraq_uinone has been prepared by tv/o methods, which have been patented. (1) From 1-oxyanthraq^uinone . (a) Ten parts of 1-oxyanthra- quinone was mixed with 60 parts of v*ater and stirred until a stiff paste v/as formed. Then 400 parts of sulfuric acid (60 Be') are added and heated at 115-120 G. After stirring a long time, a solution of 60 parts of potassium chlorate in water v/ith 60 parts of hydrochloric acid was added, and the temperature kept at 110-115. The mixture was then poured into a large volume of v/ater and pure gold needles settled out. (b) Ten grams of hydroxyanthraquinone was treated with 50 grams of acetic acid (25^) and 8 grams of sodium 6 - chlorate. The mixture was kept at a temperature between 80-100 , and 5 grams of hydrochloric acid (15^) was added. The mixture was poured into a large excess of v/ater, and the p-chloroxyanthr- quinone precipitated out in golden needles. P-bromoxyanthraquinone has been prepared by only one method up to this time. This process is patented under D. R. ?. 131403, Ten parts of erythroxyanthraquinone was placed in SCO parts of acetic acid, and a solution of 10 parts of sodium bromate was added. The solution was stirred, and 25 parts of hydrobromic acid of specific gravity 1.49 v/as added, and then V/armed for one half hour. After cooling it was poured into water, and filtered. 2-methyl anthraquinone vdiich is of importance in dying, has been prepared first and then converted into the carbonic acid of anthraquinone . The method v/hich is patented is as follows. Fifty grams of phthalic anhydride and 20 grams of toluene are mixed together, and 100 grams of powdered AlGl^ are added. HGl is evolved, and the mixture becomes warm. After 6 hours, v/ater is added, excess of toluene is distilled off in a current of steam, and the aqueous solution poured off. The cake precipitate in the bottom is made alkaline v/ith sodium carbonate, steam passed in for 4 or 5 hours, and the v/hole filtered. The filtrate is acidified whereby 2-p-toluoyl benzoic acid (m.p. 146) is precipitated. P-bromoxyanthrapuinone . 2-methyl Anthraquinone . o r 7 - This is treated with 9 parts of f-uming sulfuric acid (20^ and heated on the water hath for on e and one-half hours. Then it is poured into water and 2-methyl anthraq^uinone is ohtained-pale yellow needles, m. p. 177, and soluble in acetic acid. To 10 parts of the 2-p-toluoyl benzoic acid mix 200 parts of water and dissolve with sodium nitrate and then added to a solution of potassium permanganate, and heated for one hour on the steam bath. Then add bisulfite solution to get rid of excess permanganate and filter. White needles crystallize out, v/hich melt at 234 , The products can be crystallized from alcohol. This product is treated v/ith 200 parts of sulfuric acid (66 Be' f 0 r a few hours at 150-180, and the condensation results. The melting point is 284. P-dichloroanthraquinone . The above mentioned compound, has been preparec by convertiiig dichlorophthalic acid into dichlorobenzox^/benzoic acid, and that into dicliloroanthraquinone • This is the only method Vvh.ich is given in the literature , and all compounds which have p-dichloroanthra- quinone as these have, refer to the above method of prepara.tion . Indanthrene Byes . Vat dyes are classified in the following manner. (a) The thioindigo class derived from indigo by replacing the KH group by sulfur atoms. For example, thioindigo red, thioindigo scarlet, helindone fast scarlet, and helindone brown. All these [T 8- dyes must be enQ)loyed for cotton and wool. (b) The Giba colors are either brominated irjdigo or derivatives of the thioindigo class. Most of the Giba class of dyes may be applied equally well to animal and vegetable fibre. A few examples of this class are Giba heliotrope, Giba Green G and Giba violet. (c) The indanthrene , algole and sencole and Gibanone colors have no chemical connection with indigo, but are mostly related to anthraquinone . They require a large amount of potassium hydroxide to the hydrosulfite vat and therefore are unsuited for use with the animal fibre. It is this class of dyes v/hich I wish to give the historical background. One of the most important developments in recent years has been the production of a series of dyes known as the indanthrenes , a series of dye stuff derived from anthrquinone and possessing ex- ceptional fastness to light and to cleansing agents, such as boiling soap, and chlorine . Although first discovered in 1901, by H. Bohn of the Badische Anilin und ooda Pabrik, these dyes are now manufact- ured in twelve or thirteen shades, covering the whole range of colors from red to blue. On account of their fastness, they are largely employed in the dyeing of Sundour and other guaranteed fadeless fabrics. The first and one of the most important dyes, indanthrene blue, was obtained by fusing of an amino derivative of anthraquinone with caustic alkali, whereby tv/o molecules of anthra- quinone v/ere caused to join up and yield indanthrene blue. 9 It is necessary here to take up the action of this compound in order to have a clear uaderstanding of this series of dye stuff. If the preparation of indanthrene is carried out in the presence of reduc- ing agents, there is obtained a large amount of coloring matter, which is no good and very soluble in quinoline. Therefore, this reaction should be carried out in the presence of oxidizing agesnts. Indanthrene on reduction does not give 2-amino-anthraquinone or a reduction product of this substance. Therefore, it is not an azo derivative and there is no free amino group. They have taken place in the condensation, Alizarin is also formed, which suggests the joinhig of two anthraquinone residues through agency of the hydrogen atom in the ortho position, and the amino group. Tv/o possible formulae are; Indanthrene can not be converted into a diamine on reduction and therefore, can not have ortho-formula . Reduction of indanthrene by sodium h 3 rposulfite in the presence of alcohol gives a blue vat which contains al-kali salts of the dihydro derivative in solution. The vat v/ith zinc dust gives a yellowish-brown which is also oxidized by the air to indanthrene. The complete reduction of indanthrene with phosphorus and hydroiodic acid at El£ leads to the anthrazine . Indanthrene is a v/eak base, and forms salts with strong acids, which are dissociated with water. The two hydrogens of the imido 10 - group are readily removed "by oxidation and the base is transformed into a yellov/ish green azine , azine is readily reduced to indanthrene . The entrs-nce of halogen on indanthrene rings turns the shade toward green. Other important dyes of this series which are known are indanthrene blue G. 0., antlirafluvine , indanthrene yellow, fluvoanthrene , and indanthrene grey. Until recently none of these dyes have been manufactured in England, but in the year 1918, indanthrene blue yips manufactured by British dye limited, and placed on the market under the name of alizarine delphinol. This series of dyes, and also the sulfur dyes derived from anthraq_uinone , belong to what are called by dyers, vat dyes. The vat dye stuff from the viev; point of the chemist are classified into three groups. Anthracene dyestuff, indigoid dyestuff, and sulfide vat dyestuff. These classes in- cluded the fastest of coal tar dyestuffs at present known, though it is necessary for the reader to realize that if a dyestuff belongs to the vat series it is not necessarily possessed of the same fastness of the best members of this class. However, these are insoluble in water. Owing to the insolubility of these dyes in water, it is no possible to prepare dye baths in the ordinary manner, and for the purpose of dyeing a less direct nelhod must be employed. In using these djT-es, advantage is taken of the fact that tney are comparatively readily reduced to compounds (so-called leuco compounds) which are soluble in alkalis. The naterial to be dyed is therefore dipped in the alkaline solution of the leuco compound, now generally produced from the dye by reduction with sodium nydrosulfite , v/nich is readily taken up by both the anii!ial and vegetable fibres. On exposing the material to the air, the ■J . •■>-•- » '*• ' I < ' ' J I , I * I ■• , ' V t -' »■ •. /u: ?»«y . / ... 'A '-J > * rr- vi.^ O' . j?* » ^ 11 - oiiginal dyestuffis produced in the fibre in an exceedingly fast form, owing to the oxidation of the leuco compound by the atmos- pheric oxygen. Sometimes, the leuco compound of the dye is color- less, or very faintly colored, but in other cases, as in the case of indanthrene dyes , the leuco compound may have a very marked color, which is generally different from that of the original dye- stuff. Although, formerly vat dyeing was a somewhat difficult and uncertain process, it has now been rendered as easy and as simple as eyeing from the ordinary bath. The success of good dyeirig v/ith this class of dyes depends upon correct temperature, even dyeing, absence of unnecessary oxidation, and presence of sufficient alkali and hydrosulfite to keep the dyestuff in solution. In conclusion, this briefly covers the v/ork dene on the in- danthrene series of dyes up-to-date, and leaveo wide field for the chemist of the future to develop. v'-VyVS'X'^^ ■ ' ". ''' ' ' • ^ ' /?■•■?:';;•. -m'-'r . .r^3:a"vVf;?,^ -■'. ‘T’. 4* *'.• ■- ■■• ■'■^ i^i? v , ■‘iv . 12 - THECREIIGAI PART The theory involved in the condensation reaction is very simple. The phthalic anhydride gives np ah oxygen atom which combines v/ith two hydrogens from the ring of the benzene, and its derivatives or with the hydrogen from the ring of the phenols or their derivatives. Por example, if phthalic anhydride is condens- ed with G^qHqO in the presence of sulfuric acid, or other condens- ing reagents, the following reaction ensues. o f The most of these reactions take place in two stages. The first product which is obtained is the acid and then on heating higher, water is split out, and the carbon atom of the carboxyl group is Joined to the ring. The condensation reagents, such as AlGl , sulfuric acid, carbonyl chloride, forma.ldehyde , A1G1_ in GS , and ferric chloride all are good to take up the water. 2 The theory involved in dyeing in vats rlth the dyes msde by the use of these condensation products spoken of above, may be referred to the capacity of the dyes of forming leuco compounds of v/eakly acid properties v.lnch possess an attraction for the fibre, and are readily oxidized by air. In case of the vat colors belong- ing to the anthraquinone class this property is attributed to the presence in the molecule of carbonyl groups, v/hich by alkalirie re- ducing agents, are converted into -G-OH groups, or their soluble H alkaline salts. ± '■'. ' . A ,.L ^ ; 'I . -M ’‘-..‘^i, ••• V* .v.;‘ tf-*/' ■-■ ', .^tv * i. r ■ ■vr-;-/T% >. ..*,.1,') . - •,, ^ — » »^ - .•. • **■■•!* ' . ''* .I*'. '"'>1 '''i .''' •’• , ' ,, •' >“•. '? .^' 'J-*. I 'x iSu I .*'.. '-r . A -* _ ^■ iJLfc w. ^ "'/ * T,*^_ 'I. .. V . a.J.' 3 . *i Vr.iAi.i't :1^*y|li^f ■ 13 - exisrilis:htal part PhtAalic anhydride v/as used in all the reactions. It served as a foundation on \^ich to attach other compounds in order to form derivatives of anthraquinone . Phthalic anhydride is made commerci- ally by oxidizing naphthalene in the presence of mercuric salts with sulfuric acid. The oxidation is thus indirectly brought about by the atmospheric oxygen. The crude anhydride is separated from sulfuric acid by decanting and then is further separated by cent rifuging, and is washed free from acid. The product is dried and purified by resublimation in a pan mechanically stirred and heated over a coke fire. The first condensation reaction run was with toluene, a coal tar product which is obtained in the light fraction of oil on distillation. Ten grams of phthalic anhydride and EO grams of toluene was placed in a flask and 15 grams of i-lGl_ w'as added. 3 This mixture was heated at first upon the steam bath, and afterv/ards by flame until all the hydrochloric acid gas was given off. The contents were then cooled, and poured into two liters of water. The pmducts were recrystallized from toluene, nixed with alcohol and the yield was only 11^ of the theoretical yield. The above mentioned conditions are the best v/hich I found upon different runs. If temperature is kept too high, and if it is heated too long, one obtains a black tarry substance. i( •• ♦ ■ ■ ' ; i'* ' -V V ' ', ' * .,(k, ', i>. ■ -T '.' ' ’' /' .■ ' ■ ' 7. ■ ; ' f • ’f.®# ■ '/ -f. , ■Vj. ■ , ',. '■ i - ^^f , V.; • i 'M r . . , . , » r.it, ■ ^ >» ■ ' . W- f • t">- . , f-i :. {■ ■ , r ■ h, i! * . . ... ' '■ ^ :' L. . ys- .:•■ ; ii- v.^.v ••'.« • :<;■ J"'.' . ■; tSj ' s'- ; ' ( ■ ..-.I ^ 'V , ' ' ■ ■•' . • ' « j*? . , Ih iff ;y 4i ■ :i \ -d^'‘ ') ■ ; ,•-■'^‘• '1 !k. ■' ■ ■; * , •', ' ■■ f7.. .-J - , 1 ' 1 :■ .•■‘:, W* • a%- l! ' fVvi* ‘ il» ’ -I >. 5 '^ .‘M-.* I <‘U>' I ■ ^ J }^' • r >' , . ^ •*r ".. \ ,':''»V^i; J.'’ ’ 7 *'"'^' ' '■ - ' i ' ■'•■*. ', ■'-u. v?»;/ 2 UJ\ -T-/ " •' '**•*? ' . • , ^'V ‘- .' - '- ■ ■ ■■ , ;■■ • ' ■ ” " ( A- ; '•■■• •? ’ 5 '*' ■ ■ 'if} •'• '■■ ...■>• U^' ' , * \‘ ^ i j' h t I. .<» . *.f* 4 A. ^ rf' It . rl , 'I';’ .-J' ■;.• ■/ V ■ .1 n ‘■'■'i' c .• . 'S'v’S','?; V ' i' ' '• ' n . ,» a ; ; ti -j . i # • ♦ • 14 - This compound, v/hich. is E-p-toluoyl benzoic acid, melted at 145-147 . The --p-toluoyl benzoic acid7as heat at 120 with concentrated sulfuric acid for nine hours, and then the temperature be raised to 150 for 2 hours. After cooling the mixture was pour- ed into water and recrystallized from alcohol. The yield of 2- methyl anthraq_uinone v/as It crystallized in yellow needles and melted at 175-176 . The 2-methyl anthraq_uinone was next oxidized by heating it with sulfuric acid and potassium dichromate at 75 and finally raising the temperature to 95 ,and heat for 12 hours. The yield was only of the theoretical yield. The product was crystallized from alcohol, and the melting point was 282 . On varying the condition, I was unable to produce a larger jT-ield. The 1 supply of toluene was exhausted at this time, so I left this phase of the problem and did not return to it. j The next reac'rion which I studied was the reaction of p-cresol and phthalic anhydride in the presnece of concentrated sulfuric acid. Five parts of phthalic anhydride v/us placed in a round bottom flask and two parts of p-cresol was added with 15 parts of concentrated sulfuric acid. This mixture was heated at 130 for 12 hours. Then betv/een 180-195 for a few hours longer, and finally cooled and poured into water. This was filtered and dried. This compound 15 - was not purified because all of the soft tarry residue could not be removed. The dried product was placed in a distilling flask and zinc dust was added and the ^reduced. The contents on heating would give off a dense cloud of gas, and then clear up for a minute, and then another cloud of gas v/ould be given off. Finally the heat had to be removed in order to prevent the flask from breaking. There was considerable heat evolved within the flask. The flask was cooled and the contents was nothing but zinc dust and black crumb like substance which was carbon. The yield by this method is only 5^, and the product formed is alpha methyl anthracene. On oxidizing the alpha methyl anthracene with cromic acid in the presence of acetic acid, alpha anth raq^uinone carbonic acid -is obtained. These reactions are hard to carry out. Therefore, the temperature should be carefully v/atched and controlled. The condensation of phthalic acid v/ith the p-halogen derivative was the next field of research in which I entered. In order to run tnis series of reactions, I was forced to prepare my phenol derivatives. Formerly, p-chlorophenol v/as prepared by chlorination of phenol for IE hours at temperatuie of melting ice. This re actio;:, was carried out, but it was found that the yield was very small. / * * ■ y ' * '• ^ T jj' ' ’ * * ‘ ^ ' ,:""v/ ?K -»>,'/. w. ,y. ktl'KM. ,'; ' r y v.^- .' \- '■-7 ■ V ' ' '''\."' . 7 ■'‘t'' >' s f.Vi, ^ J .; of t'- y■^?'‘ •’■. •'itV^w'*^ 0'i/.«.Sfe ■^W®7/-,1|- _ - • . ‘ . • .u- .M • • 1. ^ W ^ • '^ . I' • -iii ' kJBMir . ’ - "* ' rji- . ^■'■. "'. / X 5‘_9 •*■•''' ^ 1 . . % ■ V. ^-. "■- -'.f ctls*. i! ,u'^>'- . • ’ I ij ?•>.'■ ‘■^ ^ 'i'': . viy‘ ^ U/,' it in ' A,'/ - if. . kX -,, . -*» »/ f \* .i ' 7. .;r •' ■ ■' - ■ .'tje •' . , ■ ' Vi ij'jrlLA j ♦•'; -' ^ , W-r-,} *A 16 - The products v/ere riDstly phenol and the ortho-chlorophenol . This reaction was handled under various conditions, and various lengths of time, but the yield was alv/ays small. The phenol had a tendency to solidify in the ice solution and stop the passage of the chlorine gas. However, this solidification v/as prevented somewhat by use of mechanical stirrers to keep the p-enol in motion. But still the yield remained low. Phenol was dissolved in carbon tetra- chloride, and thai chlorinated for IE hours, and it v/as found that the yield by this method was 30^. So this proved also unsatisfact- ory, although it v/as the hipest yield I had yet obtained. I found out that by treating phenol with SOgCl^, I could get a yield of 51^^ of p-chlorophenol . The SOgClg was irade by passing sulfur dioxide £uid chlorine alternatively into 10 grams of pulver- ized camphor dipped into an ice bath. The SOgClg v/as distilled over on the steam bath. However, the most satisfactory means of preparing p-chloropheno. was by adding 3 cc. of v/ater to every 50 grams of phenol added, and allow chlorine gas to pass through-the solution until a v/hite solid | v;as obtained. This v/as then distilled and the fraction from S17-ES5 v/as collected. The yield was 85^ of the theoretical yield. The p-chlorophenol melts at 43 C, Pifteen parts of phthalic acid v/as placed in a round bottom flask and 13 parts of p-chloro ^henol was added. Eight parts of sulfuric acid was added, and the mixture heated at 120 for 10 hours. Then the temperature v/as raisecl to 180-190 for two hours, and finally 17 - poured into water. !T he yield hov/ever, v/as only 12^^. This same glacial acetic acid, were used, hut the yield was even less. Aluminium chloride was not used because that is too expensive. The best yield which I obtained was by heating 13 parts of p-chloro- phenol with 15 parts of phthalic anhydride in the presence of con- centrated sulfuric acid for 3 hours at 150 . Then the temperature was raised to 180-190 for a few hours and finally it v/as poured into 20 ti'nes its volume of water. The p-chlorcxyanthraquinone precipitated as golden needles. The compound v/as identified in the following manx.er. It v/as fused v/ith sodium and it gave the halide test after it had been purified by dissolving in alkali and being precipitated v/ith acid. It also gave a green compound on heating with primary amines (aniline) which later turned brown w^hen the temperature v/as raised. V/hen the product was fused in a crucible it was converted into q_uinazarine . It crystallized in red needles and had a melting point of 193 G. The yield by this method is 18.5 P-chlorophenol v/as replacedby p-bromophenol and the reaction run under the same conditions as it was before , and p-bromoxyanthra- quinone v/as obtained. It formed crystals upon pouring into water, in the form of brov/n needles. The yield was 22^. Hov/ever, the reaction was not used to any great extent on account of the cost of p-broraophenol . ^^ 14 " 0 18- ?his is crystallized by dissolving in allcali and precipitating with acid . A similar reaction was run vilth aniline in place of p-chloro- phenol. The concentrated sulfuric acid causde the sulfonation of phenol which prevented the isolation of any amino -an th raq^u inone . However, a small yield of amino-anthraq^uinone was obtained by reg- ulating the reaction as in the case of p-chlorophenol , but using Alolg dissolved in instead of sulfuric acid as the condensing agent. It is very difficult to purify the amino -anth raq^uinone , and I found no means v/hich proved satisfactory. The last reaction Y/hich I made a study of was the condensation . of p-dichlorobenzene with phthalic anhydride. Ten parts of phthal- ic anhydride v/as heated at 110 with 10 parts of dichlorobenzene in the presence of 8 parts of sulfuric acid. After 10 hours, the temperature was raised to 180-190 , and kept there for a few hours, and then poured into water. This reaction v/as run similarly to the reaction described by Dr. 7/. a, Noyes in his laboratory manual for the preparation of oxyanthraq_uinone . The yield Y/as negative, and the reaction was discarded for a time. Finally, 15 parts of p-dichlorobenzene Y/as treated with 10 parts of boric acid and 100 parts of concentrated sulfuric acid, fifteen parts of pntnalic annydride v/as then added, and thoroughly mixed. The tempeiature Y/as kept at 150 for 3 hours, and then raised to 180-190 for one hour. The mixture was poured into 2 liters of v/ater, and purified by dissolving in alkali and precipitat. ing with acid. The yield was 15.5 grams fro 20 grams of phthalic anhydride and 20 grams of dichlorobenzene. T^is was ten grams more tirnn Y/hen the reaction was run without the use of boric acid. VT-^V y '.Vi" I . *■' / . . 1 w-r... ’.i 'S Yi<' ^ i I ‘- ' .’ J ''• ■ : l4 ■t ■ ^*-i- ’^■O' ■ •I ■'■'•. ’^\ i.v’'*'* •■ ■''“■^’t't^' t‘^'' * ■ c- J \‘'' ui ■■ •: :ol ■■':■!'; .A'.i ; *,iO-,'T<''..‘ y ■ ¥ ."•"’ 'V'- ' ■ '’ ' ' ’ ' if . . .. - ( A. ..<, j-.;. i.Cc P-.iH ? , *iw •!■ •■' ' .;''.0 „'.-,A ■' ■ •■■* *.,' ■.il>4*''i ,• ; /„• ! .! •*.■•' -V *M ;•■/ ’■ .•:,■■'■■ ■* '■ f ../j ‘ , ; , 1 ’■' 0't;>..L ■••. - , ■„.x.-/;^ , ■■ 'A •: - ':; ‘ji .' ■ * • ,*i ■■:>!^f ■'!/ > ■-/> ’M .>7 . , 'V .' ' t'- ' .X».« 1 *,* 4 * • / .'i« • ■‘^'A ' : . : r ^ :t -■.''' uv'-' ' ^ ^ f •< r-^ ^ w'V * 'j * ' '.>^ V • -.* -f . v^- '"'•' ^ > * * > - ’ , ,t ^ j ‘l>. ...,., - > ? '■ , ' •■ ^ \'-4\ / • . , ; , ;■ ? 'i ■ t. . - •. --j. 1 1 1 ‘ A* A^‘ 4 iiV, : -... ■t' . Vi- I? ,'■ 'V '-', '■■ C. ' - .V, ■ -•i-/.::^; / -i'. ■ v li' • ;y <• ■ : -■.. :.C ^ 7^' ■ it j'. t’,.i :} K f 1 V V >.'i ' ■ 'IS 1 . ;. i : . \a «• •L . u . i)!l'.'AJL,!. ■' J /• I ■ . n 0< « A -.If- r 19 - This product thus obtained melted at 17E . TJiis product v/as then heated with 9 parts of concentrated sulfuric acid 1C$« SO^, for four hours at 190-195 , and then poured into water. A product was obtained which gave a test for halides and had a melting point of 185 , which corresponds to the one which is given in the liter- ature for CQ^^H^CgClg. I was forced to stop my research before I v/as able to find a good means of purifying it. In conclusion of my experimental work, I obtained a 70^ yield of phthalic acid by heating phthalic anhydride with concentrated sulfuric acid for 12 hours at 110-115 G, a V V. i’ ,*■ .rA :l ' i.ff I .) r f ■ ■■■.■ • . i W.?‘. . ■‘•t w*il If .*♦• ' ■-’ .V-' i '• ■■* t‘. ' -V " . : >" • -'■ ' . ■ . ■' * ifci. .V*.' ** '* ^ ‘ * • « 'W ^ ' ' i.V'SiflH .’•<»'»■ ♦ »,'i .. j V ‘S.i* ■*■ t%i L < ' • - #■/? , '"ir t' -vS .j}i . t •?• rrr.-;- '— "■ ^« T » y T^-aftK' «u gi J i > ni . ‘ 4fc ?Tg« . '* vp r yt »r>«»? r< *n':y :>-'T'i >. i‘ EO- SmOvERY AND CONCLUSION The condition for condensation of the different products with phthalic anhydride seems to work best when temperature is kept for three hours at 150, and then raised to 180-19C, for a few hours, using sulfuric acid as the condensing agent . In all cases at least a small yield v/as obtained, and therefore it seems probable that on varying conditions, a satisfactory yield could be obtained. The presence of boric acid tends to increase the yield and make the reaction run smoother. The most promising reaction is the con- densation of p-dichlorobenzene with phthalic anhydride in the presence of boric acid and concentrated sulfuric acid. Also, the condensation of aniline with phthalic anhydride seems to be possible and this would also furnish an interesting problem to work on. It mi^t be said finally that the work on tliese intermediates is not complete by any means, but they are developed to the stage where one can take a hold of them and by careful regulation of temperature, and upon varying the conditions, be able to produce a satisfactory yield. The yields with the different compounds varied all the way from 5 to 42^. But in the case of the preparation of p-chloropheno! , a yield of 855« was obtained, and the product was a very good one. Also, phthalic acid was obtained from phthalic anhydride. The yield was 70^ of the theoretical yield. It is not worth while to discuss here again, the condition which arose in the reactions as they were discussed in the experimental if part. It may be said in conclusion that this work has proved nothing of startling importance , it has at least showed that benzene and its derivatives and phenol and its derivatives v;ill combine with phthalj c anhydride to a certain extent, and that the extent of it -iv. ’-" ^ndo n-p i -Piitm gis faivotiti gu tn 21 - BIBIIOGRAPHY Books and Serials. l."The Treasures of Coal Tar." Alexander and Smith E. "Analyses of Dyestuff." A. G. Green 3. "Dyestuffs and Coal Tar Products." Geoffrey Mortin and others . 4. "Dyeing with Goal Tar Dyestuff." G. M. Vifhattake 5 . "Artificial Dyestuff." Rimune and Wert on 6 . "Dictionary of Applied Chemistry." Thorpe III, 250 (1913) 7 . "Manufacture of Intermediate Products for Dyes." John Cannell Cain 8. "Zeitschrift fur chemie." 1867. 9. Beilstein 7,-969. 10. " 16,-54. 11. " part 3, page 40. 12. Yanino Yol. I 13.' "Organic Chemistry. " W. A. Royes 14. Berichte 33,-1900 15. " 32,-1899 16. " 6,-508 1873. Patents 17-. D. R. P. 131403 24. E. P. 975 18. D. R. 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