Iodo Derivatives of Diphenyl Ether. I. The Mono- and Certain Diiodo-Derivatives of Diphenyl Ether, and of 2- and 4-Carboxy Diphenyl Ethers¹

Abstract

Iodo Derivatives of Diphenyl Ether ous solution was acidified with hydrochloric acid and the o-nitrobenzene sulfone anilide precipitate was recrystallized twice from alcohol. The yield was 64 g. (85%). The dimethylauiline was removed from the ether layer by washing it three times with dilute hydrochloric acid, neutralizing this solution with sodium hydroxide, and extracting the free amine with ether. The ether solution was dried and distilled. The yield of dimethylaniline was 21.4 g. (85%). The ether solution containing the o-nitrobenzene sulfone methyl anilide was concentrated and a dark, dirty red-brown product was obtained which was then treated with alcoholic sodium hydroxide to hydrolyze any disulfone derivative that might have been formed from the aniline. This solution was then diluted with water and extracted three times with ether, the ether evaporated and the resuiting red-brown solid was recrystallized three times from alcohol. The yield of the pure o-nitrobenzene sulfone methyl anilide was 52 g. (74%).The two purified yields of the above o-nitrobenzene sulfonanilide and methyl anilide were then subjected to the concentrated alkali hydrolysis procedure as described previously (80 g. of sodium hydroxide and 20 cc. of water). The distillates of aniline and methylaniline were extracted with ether, dried and distilled. The yield of aniline was 15.3 g. and of methylaniline 13.1 g. The percentage yield of aniline for this reaction was 71% and for methylaniline, 70%. The over-all yield of aniline was 61.2% while that of methylaniline was 52.4%.

The Chemistry of the Diaryl Ethers.

“…The direct halogenation of diphenyl ether can be conducted in such a way that good 3rields of 4-halogenodiphenyl ethers are obtained. Chlorination is carried out in acetic acid (35) or in carbon tetrachloride at room temperature (186), bromination in carbon tetrachloride (258) or carbon disulfide in the presence of some iodine (186) or in acetic acid (34), and iodination with iodine monochloride in acetic acid (36). The 4,4'-dihalodiphenyl ethers are usually obtained in small amounts as by-products.…”

“…The 4,4'-dichloro ether is accompanied by the 3,4-dichloro compound (35), whereas the 4,4z-dibromo compound is obtained free from isomers by the bromination of diphenyl ether in alcohol (291) and serves as a solid derivative for the identification of diphenyl ether. 4,4'-Diiododiphenyl ether can be prepared by iodination of the 4-iodo compound with iodine monochloride in acetic acid (36).…”

“…Halogens can also be introduced into diphenyl ether by the diazotization of aminodiphenyl ethers and replacement of the diazonium group with chlorine (35), bromine (171), or iodine (36), or, in the case of bromine, by replacement of sodium sulfonate groups by direct bromination (259).…”

“…The nitro group in nitrodiphenyl ethers can be reduced in good yield to amino groups by means of stannous chloride (174), tin and hydrochloric acid (57), iron and acetic acid (99,185), iron and ferric chloride (64), iron and hydrochloric acid (258), alkaline ferrous hydroxide (182), zinc and calcium chloride (258), ammonium sulfide (61,183), or by catalytic reduction (36,263). The electrolytic reduction in alcoholic alkali converts nitrodiphenyl ethers to azoxv compounds which separate out, owing to their low solubility (103).…”

Synthesis of dibenzo[b,f][1,4]oxazepin-11(10H)-one and pyrido[2,3-b][1,4]benzoxazepin-10(11H)-one compounds based on o-nitrochloro derivatives of benzene and pyridine

“…[1][2][3][4][5][6] The synthesis of derivatives 7a was described in 1934; it involved the thermal cyclisation of 2-(2-aminophenoxy)benzoic acid 1a (Scheme 1). [7][8][9] This synthesis can be performed using different [10][11][12][13] esters 1a,b, and the cyclisation can be carried out in different solvents. [14][15][16] Another method for constructing the heterocyclic system of compounds 7a,b involves intramolecular aromatic substitution in 2-(o-halobenzamido)phenols, 2,4,17-19 2-(o-nitrobenzamido)phenols 2a 20,21 or 2-halo-N-(2-hydroxyphenyl)nicotinamides 2b.…”