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N \F-'P E__ the Writer Wishes to Express His Sincere Gratitude to Dr.R

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N \F-'P E__ the Writer Wishes to Express His Sincere Gratitude to Dr.R SOME IODINE DERIVATIVES 'OF RYDROXY&DIPHENYL Nl'HER AND RELATED C01fPOUNDS. by Harold S • Choguill ·· A. '.B. College of Emporia, 1927 Submitted to the Department of Chemistry and the Faculty of the Graduate School of the University of Kansas in partial fullfilment of the requirements for the degree of :Master of Arts • Approved by: ~~~ ~~ July 1931 Head of Department. &-n \f-'p e__ The writer wishes to express his sincere gratitude to Dr.R. Q. Brewster and Dr. F. B. Dains for their direction in this work, and for their helpful suggestions and advice~ T.A:BLE OF COMTE1fTS. INTRODUCTION ---------------- --- -- - - - - - 1 LITERAT'W'RE AND HISTORY OF HYDROXY DIPHENYL ETHERS - - - - - - - 2 4-Methoxy Diphenyl Ether ------------------- 3 4-Hyd.roxy Diphenyl Ether ------------------- 4 4-Nitro-4'-Methoxy Diphenyl Ether -------------- 5 2-Methoxy and Hydroxy Diphenyl Ethers - - - - - - - - - 6 Iodination of Diphenyl Ethers -------------- -- - 7 GENERAL METHODS OF INVESTIGATION OF HYDROXY DIPHENYL ETHERS - - -8 Methods of Analysis --------------------- 9 EXPERIMENTAL Preparation of 4-Methoxy Diphenyl Ether - - - - - - - - - - -11 Preparation of 4-Hydroxy Diphenyl Ether - - - - - - - - - - -12 Preparation of Benzoate of 4-E'ydroxy Diphenyl Ether - - - - - 13 Iodination of Benzoate of 4-Hydroxy Diphenyl Ether - - - - - -14 Hydrolysis of Benzoate of 5-Iodo-4-Hydroxy Diphenyl Ether - - 15 Proof of Structure of 4-Hydro:x:y-5-Iodo Diphenyl Ether - - - - 17 Preparation of Benzoyl Derivative of 4-.Amino Diphenyl Ether - 18 Iodination of 4-Benzoyl-Amino Diphenyl Ether - - - - - - - - -18 Hydrolysis of 4-Benzoyl-Amino-5-Iodo-Diphenyl Ether - - - -~: 20- Diazotization of 4-Amino-5-Iodo-Diphenyl Ether and Conversion to 4-Hydroxy-5-Iodo-Diphenyl Ether ----------- 21 Identity of Products of Diazotization and Dir.act Iodination - 22 Preparation of 4-Methoxy-5-Iodo-Diphenyl Ether - - - - - - - 23 Proof of Structure of 4-Methoxy-5-Iodo-Diphenyl Ether - - - - 25 Preparation of 4-Metho:x:y-5-Nitro-Diphenyl Ether - - - - - - - 25 Reduction of 4-Methoxy-5-Nitro-Diphenyl Ether - - - - - - - - 26 Preparation of Benzoyl Derivative of 5-Arnino-4-Nethoxy- Diphenyl Ether -------------------- 28 Acetyl Derivative of 4-Metho:x:y-5-.Amino-Diphenyl Ether - - - - 30 Iodination of Acetyl Derivative of 4-Metho:xy-5-Amino- Diphenyl Ether ----------------- 31 Preparation of 4-Metho:x:y-4'-Nitro-Diphe:nyl Ether - - - - - - 32 Reduction of 4-Methoxy-4'-Nitro-Diphenyl Ether - - - - - - - 34 Preparation of 4-Methoxy-4'-Iodo-Diphenyl Ether - - - -- - - 35 Preparation of 2-Methoxy Diphenyl Ether ----------- 37 Preparation of 2-Hydroxy Diphenyl Ether ----------- 39 Preparation of Acetate of 2-Hydro:x:y Diphenyl Ether - - - - - 41 Iodination of Acetate of 2-Hydroxy Diphenyl Ether - - - - - - 41 Hydrolysis of Acetate of 2-Hydroxy-Iodo-Diphenyl Ether - - - 43 Preparation of 2-Methoxy-Iodo-Diphenyl Ether - - - - - - - - 45 Treatment of 2-Methoxy-Iodo-Diphenyl Ether with Hydriodic Acid - - - - - - - - ~ - - - - - - ~ - - ~ - - - - ~ 46 Preparation of 4'-Nitro-2-Metho.xy Diphenyl'Ether - - - - - - 47 Raductuon of 4'-Nitro-2-1fethoxy Diphenyl Ether - - - - - - - 49 Acetyl Derivative of 2-Methoxy-4'-Amino-Diphenyl Ether - - - 52 SUMMARY Al'ID CONCLUSION ------------ -------- 53 Bibliography ------------ - - - - - ~ - - - - 54 1 SOME IODI1Y.E DERIVATIVES OF HYDROXY DIPHENYL ETHER AND RELATED COMPOUNDS. ImRODUCTION The work embodied in this thesis was carried out in a systematic study of some of the iodine derivatives of eertain substituted diphenyl ethers. In 1927 Harrington and Barger1 • .. i proved by synthesis that thyroxin was a derivative of diphenyl ether. r r ll Nfl~ ~o Ho- -o- e.-e..-C.... 01-\ ~ H 0r OL Since that time, study has been made to determine the active principle of that substance. The work carried on in this institution consisted in researches in ~he iodine derivatives of carbo:xy and amino diphenyl ethers. The study of the iodine derivatives of hydroxy diphenyl ether was another of this series of investi- gations. Two series of hydroxy diphenyl ethers were studied in this investigation~· Series A: Derivatives of 4-bydrolcy' diphenyl ether, or of para-phenoxy-phenol~ 0-o-O-OH 2 Series B: Derivatives of 2-hydroxy diphen;yl ether, or ortho-phenoxy phenol. Series A included study of derivatiyes of two types: those in which the substituting group entered the same benzene nucleus with the hydroxyl group; and those in which the substi- tuting group entered the other benzene nucleus than that hold- ing the hydroxyl group. As an example of the first type oA-x 0- V-GH Asan example of the secmnd type x-0-0-0-oH 3 LITERATURE AND HISTORY OF HYDROXY DIPHENYL ETHERS. 4-HYDROXY Al'ID 4-1VfETHOXY DIPHENYL ETHER In literature, three methods are given for the prep- aration of 4-llydroxy ether, two of which depend in their production from the corresponding methoxy ether. I. Diazotization of 4-amino-diphenyl ether and con- version of the amino group to hydroxyl by treatment with hot 50% sulfuric acid. II. Fusion of the alkali salt of the monomethyl ether of hydroquinone with bromobenzene at a temperature of 240° for 2ra hours, and comversion of the methoxy group to hydroxyl by refluxing the ether with anliydrous aluminum chloride in benzene solution for 2 hours. III. Fusion of the potassium salt of phenol with p-bromoani~ol~ at a temperature of 200-210° for 4 hours, and conversion to the hydroxy ether by refluxing with aluminum chloride in benzene solution for two hours. Of these methods, diazotization of 4-amino-diphenyl ether results in poor yields and a large amount of tarry mat- erial. Consequently, preparation from the corresponding methoxy derivatives is both more convenient and economical. :METHOXY-DIPHEUYL ETHER In preparation of 4-metho=cy-diphenyl ether, Robinson2 used the potassium salt of the mono-methyl ether of bydroquinone in fusion with bromobenzene, using a slight excess of the phenol ether. He describes the substance as a 4 thick yellow oil which .distills with steam. The boiling point recorded was 186° at 32rmn. One hundred per cent yields were obtained by this method. Oesterlin3 employed the potassium salt of phenol ( f2 mols) with :p-bromo-anisole. The boiling point is the same as that given for Robinson. However. Oesterlin does not give yields in his article. In this thesis, Oesterlin's method was used with a few modifications for the preparation of methoxy-diphenyl ether. The p-bromoanisole vms obtained in almost quantitative yields by the direct bromination of anisole in glacial acetic acid. 4-HYDROXY DIPHENYL ETHER. In order to obtain the corresponding hydroxy ether from 4-methoxy-diphenyl ether, Osterlin dissolved the oil in benzene, refluxing this solution with anhydrous aluminum chlor- ide for two hours. The phenol was set free from its aluminum salt with concentrated acid and the benzene layer extracted with alkali. The product was precipitated from its alkaline so- lution with hydrochloric acid. In investigation, two other methods were found to give the hydro:xy eompomid. The most successful vra.s the general method of breaking alkyl ethers by treatment with hydriodic acid. Raiford and Colbert4 found that concentrated hydro- bromic acid removed the alkyl group from alkyl-phenyl ethers, but that diphenyl ethers were unchanged by this treatment. For this reason,. bydriodic acid was employed giving almost 100% yields of hydroxy diphenyl ether, without the ·phenyl ether 5 bonding being ruptured. The other method was direct fusion of methoxy diphenyl ether with anhydrous aluminum chlorfde. This resulted in the rupture of both ether bondings contaminating the product with phenol, thus making it unsuitable. Details of the method used will be given later. Some study of had been made of 4-methoxy and 4- bydroxy-diphenyl ether in England and ·in Germany. Robinson5 nitrated 4-methoxy-diphenyl ether in glacial acetic acid solution, obtaining 3-nitro-4-methoxy-diphenyl ether. The substance erystallized from alcohol in yellowish white crystals melting at 73°. He also produced 4-hydroxy-3-nitro ether by refluxing the nitrated methoxy compound for 60 hours in a copper flask. This product was a yellow solid of melting point 51~520. It was found in later work, that the same pro~ duct could be obtained by careful fusion of 3-nitro-methoxy- diphenyl ether with aluminum chloride for 1 hour at 130°. The product obtained crystallized from petroleum ether in yellow needles, was soluble in alkali, and gave the same melting point, 520, as the compound described by Robinson~ Qsterlin6 recently carried on a stua.Y of hydroxy diphenyl ether as a source of making more complex ethers. Some of those prepared were and CH3o-Q-o-<=)ao-Q 6 4-NITR0-4LMETHOXY DIPHENYL ETHER. Oesterlin7 also studied 4-nitro-4~methox.y-diphenyl ether which he prepared by fusion of p-chloronitrobenzene with the potassium salt of the monomethyl ether of hydroquinome, according to the reaction He reduced this compound to the corresponding amine by the action of glacial acetic acid with iron powder. However, he makes no mention of the preparation of 4-bydroxy-4'-nitro- diphenyl ether; 2-METHOXY Alill HYDROXY DIPHElITL ETHER. In regard to 2-hydroxy-diphenyl ether, little work is recorded. Ullmann and Stein8 prepared 2-methoxy ether and 2-2'-dimethoxy diphenyl ether. The monomethyl ether was pre- pared by fusion of the potassium salt of gu.aiacol with bromo- benzene. A second method employed the fusion of the potassium salt of phenol with o-l>romoanisole ~ The first method gave better yields than the second. 2-Bydroxy-diphenyl ether was prepared from 2-methoxy by refluxing with anhydrous aluminum chloride in benzene solu- tion for two hours. 2-2'-Dimethoxy ether was likewise converted · to the hydroxy ether and made to diphenylene oxide. 7 IODINATION OF DIPHENYL ETHERS. A number of iodination products of diphenyl ether have • been prepared of derivatives other than the :hydroxy ether. Those prepared by Scarb~rough9 include 4-iodo-4'-nitro, 4-iodo- 4'-acetamido, 4-iodo-4'-amido, 4-4'-diiodo diphenyl ether.
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