AZOBENZENE-p -PHENYLHYDRAZINE SULFONIC ACID AND ITS REACTIONS BY WALTER FRED STRAUB THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE IN CHEMISTRY COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1918 UNIVERSITY OF ILLINOIS *3 June 1 8 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Walter.. .Zred...S.traub..... ENTITLED....Aj5Sfo.8tt3.e^^ actions IS APPROVED BY ME AS FULFILLING THIS P ART OF THE REQUIREMENTS FOR THE „.S ie , C h i t ry, DEGREE OF £a or .. of c n c e ... in em s Instructor in Charge HEAD OF DEPARTMENT OF TABLE OF COUNTS Page PART I. I Introduction 1 II Historical Part 3 III Theoretical Part 7 (A) The Reaction of the Formation of Azobenzene- p-phenylhydrazine Sulfonic Acid 8 (B) Condensations of the Red Acid 1. With aromatic aldehydes and ketones. 9 2. With aliphatic aldehydes and ketones. 10 3. With sugars to form osazones, 11 4. With acetoacetic ester. 12 5. With dihydroxytartarie acid. 13 IV Experimental Part 14 (A) Preparation of Azobenzene-p-phenylhydrazine Sulfonic Acid 14 (B) Identification of the Acid. 15 (G) Preparation and Analysis of: G H 01 18 18 22W H 1I 18 °30 30 8 4 -' G H 1J ^ ma:1 tose condensation) 19 36 40 8°9 ( lac1;ose condensation) 20 G 36H40%°9 21 C 1SH20H4°2 21 C18HS0°2H4HC1 (D) Condensation with Dihydroxytartarie Acid 22 1. Preparation of dihydroxytartarie acid 22 2. Condensation in glacial acetic acid solution 23 Y Summary 24 PART II. Some Rosin Compounds 26 Rosin derivatives prepared "by: 1. Chlorination of molten resin (catalysts) 2. Fusion with certain inorganic substances 3. Hydrogenation 4. nitration followed by sulfide reduction BIBLIOGRAPHY 30 Digitized by the Internet Archive in 2014 http://archive.org/details/azobenzenepphenyOOstra AGOQWLEDGMENT The writer wishes to express his apprecia- tion to Dr. Roger Adams for his constant inter- est and helpful suggestions during this investi- gation. (1) P A 3 T I. (2) AZ0B3HZEKE-P-PHEEYLHYJHAZIIIE SULFONIC ACID I. IKTHODUCTIOH . This problem arose in connection with the commercial manufacture of phenylhydrazine in the organic laboratories of the University of Illinois. The ordinary methods of preparation embodying the reductioi of diazobenzene with stannous chloride and hydrochloric acid, with zinc and an acid, treatment with sodium acid sulfite and subsequently zinc and acetic acid, and reduction with tin and hydrochloric acid, were tried and gave very poor results. In considering a better meth- od it was thought that sulfur dioxide might convert the benzene diaz- onium chloride into phenylhydrazine sulfonic acid which could then be decomposed to yield the free hydrazine. The fact that sulfur dioxide acted as a very efficient agent in the reduction of bromine to hydro- bromic acid, and also in the preparation of hydroxylamine from ni- trous acid suggested its use in this case. Upon introducing sulfur dioxide into a benzene diazonium chlor- ide solution a deep red compound separated out. As the literature held no satisfactory explanation for this reaction an investigation for the purpose of identifying the compound was begun. (3) II. HISTORICAL PART . From a preliminary examination of the red compound which had "been formed upon the introduction of sulfur dioxide into benzene di- i azonium chloride, there was suggested the work done by Kbnig on a reaction of this nature. KCnig treated an acid solution of benzene- diazonium chloride with a concentrated water solution of sulfur diox- ide at CP and observed that a red color gradually developed which re- sulted after some hours in the separation of a deep red solid. The solid separated out in voluminous flakes which upon filtering and washing with alcohol finally gave a dry, red powder. Xonig extract- ed this product with boiling chloroform, adding some bone-black. Prom the extraction a white plate-like mass of crystals was obtained whicl The compound from analysis had apparently the formula C 12H12%S02 . acids, dilute alka- was found to be insoluble in cold water, dilute chloroform, acetone, lies, and soluble in hot 'water, alcohol, ether, It did not give the etc. It reduced Fehling's solution on boiling. and from the compari- Liberrnann reaction. Prom his analytical work 2 Emil Fisher in causin, son with the hydrazine derivative prepared by KBnig concluded phenylhydrazine to react with benzene-sulfochloride , further evi- C H miHS0 C H . For that the compound was a hydrazine 6 5 2 6 5 a benzene diazonium dence, he synthesized the same compound from C H S0 H, then reducing the salt reacting with benzenesulf inic acid, 6 5 2 hydrazine with zinc dust resulting diazobenzene sulfinic acid to the In his conclusions from the and acetic acid in alcoholic solution. main product obtained investigation he assumed, apparently, that the chloride with sulfur dioxide from the treatment of benzene diazonium of part of Konigs . The repetition was the hydrazine ^E^mm30 z 6E 5 could be no more than a side work proved to us that this hydrazine had thrown no light upon the product in the reaction, and that it (4) nature of the red compound. After a complete analysis had given us the C I\r empirical formula 1 gH11 4S03lIa for the yellow sodium salt of the red acid, and a reduction of the acid itself had given a clue to its structural formula, we could then review the literature systematical- ly. It was found that Troeger had prepared the same red acid by a method differing somewhat from that used here. By diazotizing ani- line in a dilute sulfuric acid solution and then saturating- with sul- fur dioxide, he obtained the red compound with two side products. Troeger purified the acid by means of its ammonium salt and analyzed the free acid. Our analytical results were obtained from the reerys- tallized sodium salt. Troeger proved the structure of the red acid to be CgHgN:lI.GgHgliIHHHSOgH. His proof rested upon the decomposition products obtained upon reduction with zinc and acetic acid. These products were aniline CgHgNHg, p_-phenylene diamine, NEgCsH^THg, and ammonium sulfate. He also synthesized the acid by treating diazo- tized amidoazobenzene with potassium carbonate and potassium sulfite, adding ammonium sulfide to the potassium salt of azobenzene-diazosul- fonic acid CgHgN :1JC 6H4N :lISOgK (which had formed in the first step) and freeing the azobenzene-p-phenylhydrazine sulfonic acid with hyd- rochloric acid. The second step: C5H5IJ ilI.CgH^.H :HSOgK to CgHgBiIJ.CgH^IIHUHSOgK took place easily when ammonium sulfide was added. When the hydrazine acid, on the other hand, was treated with ammoniacal silver nitrate or copper sulfate the latter reaction was reversed and the respective silver and copper salts of azobenzene- diazosulfonic acid were formed. Troeger attempted to improve his method of preparation of azo- benzene p-phenylhydrazine sulfonic acid by diazotizing aniline sul- (5) fate with amyl nitrite. This was done in glacial acetic acid solu- tion with subsequent saturation with sulfur dioxide. The method, how ever, yielded only the sulfazid CGH5NHNHSO2C6H5 and consequently was abandoned. Following these experiments, Troeger extended his investigation to a further study of azobenzene-p_-phenylhydrazine sulfonic acid. G 12H llK4S°3H(GgH5M2) was prepared^, and also the para toluidine and para xylidine salts. The action of nitrous acid upon azobenzene-p- phenylhydrazine sulfonic acid was found to yield the compound GsHsNiHGgj^lJ^ which stannous chloride reduced to aniline, p-phenyl diamine, and nitrogen. Troeger next studied the condensations of the red acid with cer- tain aldehydes and ketones. He worked first with aromatic compounds and later took up certain ones of the aliphatics. Condensations in alcoholic hydrochloric acid or in e:lacial acetic acid gave, respect- ively, the sulfate or hydrochloride addition products corresponding to the aldehydes used. With benzald ehyde , G^HsCHO/he obtained the hydrochloride C 5H 5N : IJC 5H4NEN : CHC5H5.HCI. Chloro benzald ehyde , bromo- benzaldehyde, p-aminobenzaldehyde , hydroxybenzaldehyde, furfuralde- 7 hyde, etc., were tried and yielded sulfate addition products from which the free hydrazone was liberated by addition of ammonium hydrox- ide. In all cases the free hydrazones were yellow or reddish yellow crystalline products while hydrochlorides or sulfates of these hylra- zones were dark blue in color but also of crystalline structure. II mention was made in any of Troeger 's publications in regard to the possibilities of using these compounds as dyestuffs. Troeger also studied the condensations of several aliphatic al- dehydes and ketones with azobenzene-p-phenylhydrazine sulfonic acid. (6) He found these condensations to proceed even more easily than did the aromatics, but the isolation of the free hydraaones gave great diffi- culty on account of their solubility. Such was also found to be the case in the present work with, the sugars. Troeger obtained hydra- zones with acetone, acetylacetone , chloracetaldehyde , and ethylace- toacetate. With dextrose in alcoholic hydrochloric acid, he prepared the hydrochloride C^QHggOglJ^HCl but was unable to isolate the free hydrazcaie. He did not attempt to apply azobenzene-p-phenylhydrazine sulfonic acid to the general reactions with the sugars. (7) III.'iiiEOaSTICAL PA:\T When it was decided, in the organic manufacturing division of the University of Illinois to attempt the preparation of phenylhydrazine through its sulfonic acid by saturating benzene diazonium chloride with sulfur dioxide, the earlier work of Kt5nig seemed at first thou^it to eliminate this proposed method. KBnig had treated benzene diazon- ium chloride with a saturated water solution of sulfur dioxide and had obtained a deep red compound formed by a coupling reaction. On extracting the red compound with boiling chloroform Kbnig obtained a white crystalline hydrazine Cg^HHilHSC^CgHg which he apparently con- cluded to be the main product of the reaction.