A STUDY OF OXAZOLON AND PENTOXAZOLON RINGS AND THEIR DECOMPOSITION PRODUCTS BY CHARLES WILLIAM RODEWALD THESIS Submitted in Partial Fulfillment of the requirements for the Degree of MASTER OF SCIENCE IN CHEMISTRY IN THE COLLEGE OF LIBERAL ARTS AND SCIENCES OF THE UNIVERSITY OF ILLINOIS 1921 * \ 'O UNIVERSITY OF ILLINOIS THE GRADUATE SCHOOL Jul y . 30, 192l_ I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Charles 7illiara Hodev/ald ENTITLED A study ^' T TcyAZQT rv T D^COirQCTTICTT ^OTXTCTS. BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF faster of Science in Chemistry . Recommendation concurred in* Committee on Final Examination* ^Required for doctor’s degree but not for master’s 47698? ■ ACMOWLEDGMSETT . The writer desires to take this opportunity to express his appreciation of the guidance and help given by Dr. Roger Adams in the preparation of this the si s . Digitized by the Internet Archive in 2016 https://archive.org/details/studyofoxazolonpOOrode IXTD3X Fage . A STUDY OF OXAZQLOII AIO EMTOEAZOLOII RINGS AETD THEIR DECOH* POSITION PRODUCT 3. Introduction . . Historical Theoretical Experimental . . . TIE USE OF CHLORAMINE T AGEUT3. 1 2 3 5 DIOHLORAMINH T v: 0 HLOE IN AT IH G Introduction 9. historical . . 10. Theoretical 11. Experimental .... 12 . A STUDY OF COMPOUNDS SIMILAR TO D K. Introduction 15. Theoretical 16. Experimental 17 . THE R 1PARATI0K OF TROPIC ACID BY THE REDUCTION OF FORMYL PHEUYL ACETIC ESTER. vl 20 *T ’ 2 HISTORICAL. There has not been a great deal of work published on oxazolon and pentoxazolon ring compounds. ITemirowshy made >S-chlore thy 1 chlor carbonate from phosgene and ethylene chlorhydrin. 3 y condensing this with aniline, he made the yS- chlor ethyl ester of phenyl carbaminic acid. J e then made H-phenyl oxazolon by treating the ester with alhali. Otto"- made '7-phenyl oxazolon in a different way. TJ e condensed ani- line with ethylene chlorhydrin to fora hydroxy ethyl anilihe and then treated this compound with phosgene. • ' . * • - . r • ; ■ 3 TiiGQRGTlCAL. Gxazolon and pentoxazolon rings ars formed b: the condensation of -chlor esters of chlor carbonic acid with primary aromatic amines. The products of this condensation are derivatives of carbaminic acid. .hen these carbaminic acid derivatives are treated with excess alkali in solution, 'TCI splits out of the side chain and a ring compound is formed. hen chlorethyl chlor carbonate is used, the ring compound formed is a derivative of oxazolon and when chlorpropyl chlor carbonate is used, the ring compound is a pentoxazolon derivative. The reactions involved are as follows; SENHg +■ Cl-CQ-O-CHh-GHg-Gl -*• BHH-CQ-O- JHg-C . - Cl -t- iu . *::ci. ThiZ-CO-O-Gh^-CK— Cl f I'OIf. - — * hC \ ch 2 -ch 2 The amines used in the preparation of the ring compounds were ani- line and p-chlor aniline. ‘ /S -chlorethyl chlor carbonate was made by passing phosgene into elthylene chfhorhydrin . r -chlorpr 1 chlor carbonate was made by passing phosgene into trimethylene chlorhydrin. The condensations between the .romatic primary amines and the chlor esters of chlor carbonic acid were carried out in water suspension. The carbaminic acid derivatives thus formed were white crystalline solids soluble in the ordinary organic solvents and usually crystallizable from one of them. The formation of the ring compounds from the carbaminic acid deriv- atives was brought about by refluxing the latter with four or five moles of alkali in concentrated aqueous solution. The preparation of the amino alcohols was attempted by first isolating 4 . the ring compounds and then hydro li zing them; and also by prolonged treat- ment of the carbaminic acid derivatives with KOH solution. "XPERIIOTTAA. ..reparation of /^-chlorpropyl Chlor Carbonate. 94 g. of teimethylene chlorhydrin were placed in a bottle surrounded by ice and salt. Phosgene was passed through in a stream of bubbles, (slow enough to be counted) until the weight remained constant. The in- crease in weight was about 80g. A rather narrow bottle was used so that the phosgene -ould have greater opportunity to react with the chlorhydrin. A calcium chloride tube was used in the tube carrying the gas out of the bottle to prevent water from getting into the reaction. About six hours were required to pass in the phosgene. After the phosgene was all passed in, the bottle was al loved to warm to room temperature and the contents were poured into a 500 cc . flash fitted with a reflux condenser with a calcium chloride tube in the top. rv he mixture was refluxed for an hour or two until no more HC1 or COClo was given off. The mixture was cooled and washed once with a 5f* solution of sodium carbonate and then twice with distilled water. The product was then distilled. Boiling oint, 178-80. Yield, 70-75/!. Preparation of f -chlorpropyl Ester of p-Chlorphenyl Carbaminic Acid. To lo4 g. of p-chlor amiline, 500 cc. of water are added. 75 g. of /^chlorpropyl chlor carbonate are added in portions of 5 cc . The reaction mixture is shaken vigorously after each addition. After the last of the chlorcarbonate has been added, the reaction is allowed to stand for 12 hours or more. The water layer is separated in a separatory funnel and the oily layer poured out into a beaker. This is ashed with a lop solution of HC1. Upon washing wi th HC1 the product becomes solid. It is filtered off, washed with v/ater, and dissolved in 300 cc. of ether. 6 The ethereal solution is dried over calcium chloride. 150 cc . of ligroin are added and most of the ether is evaporated off on the steam bath. On cooling, the product crystallizes out in white needles. Yield 70^. Melting Point 52-. ! 3°. In preparing the r -chlorpropyl ester of phenyl carbaminic acid by condensing aniline with A chlorpropyl chlor carbonate, difficulty was experienced in getting the product in a crystalline form. It is necessary 4 to wash out all traces of the aniline with dilute /"Cl. Preparation of IT p-Chlorphenyl Pentoxazolon. 5 g. (One mole) 'of the carbaminic ester and 5g. (6 moles) of EDH were refluxed with 50 cc. of water for one hour. The mixture was cooled and extracted w ith 100 cc. of benzene. About half of the benzene was evap- orated off and the pentoxazolon was precipitated, on cooling, by adding ligroin. The crystals were filtered off, dissolved in benzene and re- precipitated. The product was then dissolved in hot water and allowed to crystallize out. The product should be white. If highly colored it may be boiled with a little bone black. r 'he yield of purified material was 45 ^ of the theoretical. Melting Point, 113-114°. 7 reparation of the Amino Alcohol. 5 g. of the /"^chlorpropyl ester- of p-chlorphenyl carbaminic acid were refluxed eight hours with 5 g. of KOH in concentrated acueous solution, in an attempt to carry the reaction through to the amino alcohol without isolating the pentoxazolon as an intermediate. The result was a mixture of an oil and a solid. ITo definite compound was isolated. 10 g. of II p-chlorphenyl pentoxazolon were refluxed for five hours 7/ith eight grams of KOH in 75 cc. of water. A heavy oily product resulted. It was washed with water and distilled under diminished pressure. The boiling point was 205-211 at 18-20 mm. pressure. This was probably the . . . . . ' . ,i . 1 ; ■ ; ' ■ i . . • , ... » . . I 4 . _ . . . ■ ) 7 amino alcohol. Cl S GH ? - C H ? - CH 0 OH . ri his compound was not prepared in sufficient quantities for analysis. At this point the supply of phosgene gave out and the work was abandoned. Attempted ''reparation of Phosgene. .In attempt was made to prepare phosgene 'rom CCl^ and fuming sulfuric acid. 100 cc. of CCl^ were heated to brisk boiling. A 2 Ft. air condenser with a water condenser above was used as a reflux condenser. 120 cc . of fuming sulfuric acid $20~ excess SO r/ ) were allowed to flow slowly down the condenser. The odor of phosgene was apparent but it was not formed in any qu-ntity. It is probable that the fuming sulfuric acid used did not contain 3 O 3 in sufficient excess for this preparation. ,x * ■ V ' ' 8 aomaKY. /^■chlorpropyl chlorcarbonate will condense with primary aromatic amines to form esters of substituted chlor carbarainic acids, “.'hen these esters are refluxed with alkalis, HC1 is split out and ring compounds are formed. ".Tien these ring compounds are further treated with alkali, they are hydrolized, carbon dioxide is split out, and amino alcohols are formed. * • ■ a: ' 'I- . • , ' t ... * 9 . THE USE OF CHLORAMINE T AND DI CHLORAMINE T AS CHLORINATING AGENTS. -o- INTRODUCTION. During the war, facilities were developed for making the N-chlor derivatives of p-toluene sulphonamide . They were used as antiseptics, their antiseptic action being due to their property of giving up chlorine in the presence of organic matter. It was thought that these compounds might be valuable in chlorinating various organic compounds in cases where the chlorination was more or less difficult to control. It was the object of this work to investigate the use of these compounds as chlorinating agents. They ?;ere tried out in the chlorination of phenol and acetophenone. 10 . HISTORICAL. nr Chloramine T and dichloramine T were prep .red by Chattaway/' in the course of an investigation which covered a large number of the nitrogen halogen derivatives of the sulphonamides . Dakin^ has done a la-ge amount of work on the p eparation and use of chloramine T and dichloramine 1 as antiseptics. . 11 cWa THEORETICAL cH. '3 Chloramine T is and dichloramine T is 0 The former is soluble in water and the latter in various organic solvents. They give up chlo. ing ’quite readily to form p- toluene sulphonamide . Their use as chlorinating agents would have an advantage in that the exact amount of chlorine present could b* determined and also the addition of chlorine to any reation mixture could be cade as slowly as might be desired. ,lso the chlorine liberated from these compounds, being in a somewhat nascent state might have some selective action which free chlorine would not possess. .. i SXPSRIIOSITAI. 1 . 2 . Chlorination of Phenol. 94 ‘g. of phenol were dissolved, in one liter of water. 282 g. of chloramine T were added. The reaction was allowed to proceed at room temperature. Crystals of p-toluene sulphonamide soon began to appear. After four hours the solution was filtered and then extracted with ether to remove all of the sulphonamide. 168 g. (97.5^ of the theoretical) of crude p- toluene sulphonamide were recovered. The solution of phenol 7 /as alkaline at this point. It was acidified with HC1 md an oil separ- ated and settled to the bottom. This was separated from the acueous layer and distilled. On distillation, 20 g. of p-chlor phenol md 32 g. of o- chlor phenol were obtained. Chlorination of Aceto-phenone An attempt was made to use dichlorarnine n in alcoholic solution but the solution in alcohol was entirely too unstable and on exposure to sunlight or on slight heating, chlorine was rapidly evolved. 50 g. of aceto phenone were pi ced in a flash fitted with a reflux condenser and heated to 80° in the direct sunlight. 58 g. of dichloramine T iissolved in 250 cc. of benzene were then added in a slow stream through a separatory funnel. The solution was kept boiling. The solution of dichlorarnine T in benzene must be kept cool or chlorine will be evolved. The refluxing was continued for n hour after the addition of the chlor- amine. 125 cc. of benzene were distilled off and the mixture cooled in ice md salt. p-Toluene sulphonamide crystallized out and was filtered off, and washed with a little cold benzene. The filtrate and benzene washings were washed t- ice with a cold solution, (10 f.) of ITaOH. The sol- ution was then dried over calcium chloride. Part of the benzene was dis- tilled off and -chlor aceto phenone crystallized out. Yield, 40" . • ’ L ■S'. . . . . - . ' . . . ' ' # ; • . J , . . r ' ■ y -•c r r. . ... 1 .> t i ... •• ■ .. • . . " . . - i. ■ T • ,-J 15 Friedel and. Craft’s reaction 'ith Dichloramine T. It was thought that it might be possible to form the IT-diphenyl derivative of toluene p-sulphonamide by treating dichloramine T with benzene in the p esence of AlCl*; 75 g. of AlCljj and 200 cc. of benzene were placed in a one liter flask. A solution of 120 g. of dichloramine T in 200 cc. of benzene was added in small portions. There was quite a vigorous reaction, in which chlorine was given off. The reaction was allowed to proceed at room temperature, '.'/hen the reaction had subsided, the mixture was re- fluxed for hours. The reaction mixture was pjrared out into cold water and divided into t :o portions. One portion was acidified with sulfuric acid and steam distilled. Benzene, monochlor benzene, and toluene p- sulphonamide were obtained in the distillation. The other portion was made strongly alkaline with PaOH and steam distilled. Benzene and mono- chlor benzene came over. In all, 51 g. of monochlor benzene and 259 g. of benzene were obtained In the distillation, indicating that none of the benzene had reacted with the dichloramine T to give the compound desired. 14 "ULEklARY . Chloramine T and dichloramine T were used respectively in the chlorination of phenol and of acetophenone. Chlorination with these rea- gents sh07/ed no particular advanta e over the use of free chlorine. An unsuccessful attempt was made to prepare the IT-diphenyl derivative of toluene j^-sulphonamide hy treating dichloramine T with benzene in the presence of AlCl^. . ' : 15 . A STUDY OF COMPOUNDS SIMILAR TO D M. During the war the compound <0 , known as D M, was made ^ A *'C/ by condensing diphenyl amine with arsenic trichloride. It was thought that similar compounds mi^it be made by condensing other compounds con- taining two phenyl groups with arsenic trichloride. T n this work such ■v condensations were attempted with carbazole, benzidine, phenanthrene, and diphenyl . 16 THEORETICAL. The condensation product between AsCl^ and diphenyl amine was easily obtained by merely treating the dipnehyl amine with the chloride either with or without a solvent. In the cases where a solvent had been used, the solvent was xylene. The reaction was as follows: O-w-o ^ t-zt/c/ i '-c/ In the present work, each of the substances used was tried in xylenfc solution, and without a solvent, and in every case without and with AlCl* as a catalytic agent. There were no indications of condensation in any case. In all instances where no solvent was used, the mass carbonized when heated with A1C1* and the result was merely ch rcoal. ' 17 . EXPBEIBMTAL. Condensation of Arsenic Trichloride with Carbazole. 12 g. of sublimed cargazole were laced in a small flash with 13.5 g. of A1C1- and heated in afc oil bath at 170-180° for four and one-half hours. The reaction mixture was poured into water and a small amount of rTCl added. The solid which separated on firing the mixture into water was filtered off. It was unchanged carbazole. 24 g. of carbazole were dissolved in 175 cc.of xylene. 27 g. of AsClg were added and the mixture refluxed for five hours. Tiere was no reaction as shown bp the fact that no HC1 was evolved. 19 g. of AICI 3 were added and the mixture was again refluxed. A solid began to separate out. After about 20 hours no more 101 was evolved. Tie reaction was cooled and poured out into cold water. A little HC1 was added and the mixture filtered. The solid product was washed with ether by grinding in a mor- tar unde: ether. The ether was filtered off. The product proved to be carbon. AsCl'r, AlCl^ and carbazole were also heated together in molecular propo tions without a solvent, In this case also the mixture carbonized. Condensation of Arsenic Trichloride with Benzidine. Practical benzidine was purified by dissolving in the theoretical amount of 20 HC1 and then precipitating with ITaOH. The substance thus obt ined was dried in an electric furnace at 90-100°. 20'-. of benzidine were heated on an oil b..:th at 150° with 20 g. of AsCl^ for four hours. The mixture was then treated with 150 cc. of water and 2 cc. of concentrated HC1 were added. The arsenic was precipitated while hot, with H?S. The As was filtered off and the filtrate made alkaline with ITaOH. There w s a copious precipitate whi h proved to be benzidine. Melting ~oint 124-135°. It was soluble in TJ C1 and insoluble * - \- y : 18 . in an excess. 20 g. of benzidine were dissolved in 100 cc. of xylene and brought to boiling under a reflux condenser. 20 g. of AsGl^ were added drop by drop. In this case also the benzidine was recovered unchanged. The above condensations with benzidine were attenpted using Aid., as a catalyst. In both cases the mixture carbonized. Oondensati ns of Arsenic Trichloride with I henanthrene and Diphenyl . Txactly similar reactions were attempted with diphenyl and with phenanthrene. In all cases the results were similar to those obtained with carbazole and benzidine. . 19 . SUmUET. Condensations between AsClr. and various compounds containing two phenyl groups were tried. T t mi ght he expedted that two moles of 7 Cl would be split out giving a five or a six membered ring with an arsenic atom in the ring. Che condensation -as tried with carbazole, benzidine, phenanthrene , and diphenyl. n here was no condensation in any case. - - i . * ' - -*• T • . ! . . • 20 THE PREPARATION OF TROPIC ACID BY THE CATALYTIC REDUCTION OF FORMYL PHENYL ACETIC ESTER. 7/islicen.us has prepared tropic acid by the reduction of phenyl formyl acetic ester with sodium amalgam. r, he object of this research ■”•••. s to perform the reduction catalytically using hydrogen as the reducing agent and platinum black as the c talyst. The ethyl ester of formyl phenyl acetic acid was prepared b^r the 5 same method used by "lslicenus for tne preparation of the methyl ester. ;thyl formate was used instead of methyl formate and ethyl phenyl acetate instead of the methyl ester. he yield was 39 r of the theoretical. The boiling point was 157-165 at 30 mm. 10 g. of the formyl phenyl acetic ester were dissolved in 7o cc. of alcohol and shaken for 36 hours with one gram of platinum black in an atmosphere of hydrogen under 30 lbs. pressure per square inch. ITo reduction took place. This was shown by the fact that no hydrogen was absorbed, the pressure remaining constant throughout the entire time. \ \ \ \ ' ■Vi . . ■- • i ' * : 21 BIBLIOGRAPHY. 1. J. : r. Chen. (2) 31, 174. 2. J. Pr. Chen. (2) 44, 17. 3. J. Chem. Soc. 87, 145. 4. 3aMn £ Bunham: Handbook of Anti septios, 28-47. 5. Ann. , 415 , 229.