Dipheyl Etherを基核とするAcid Hydrazide誘導体の合成研究 (第12報)

Abstract

Hydrazinolysis with hydrazine hydrate was examined with mononitro-monoamino-diphenyl ethers possessing one each nitro and amino group in each benzene ring. In compounds with nitro group in the position ortho to phenoxyl group, hydrazine hydrate effected cleavage of ether oxygen to form o-nitrophenylhydrazine (II) and the corresponding aminophenol derivative (III). (II) easily underwent dehydration to form 1-hydroxybenzotriazole (IIa).In compounds with the nitro group meta to phenoxyl group, (IV) resisted hydrazinolysis, either at ordinary or higher pressure, and only reduction of the nitro group occured to produce a diamino derivative (V). In the case of compounds with a nitro group para to phenoxyl group, (VI) resisted hydrazinolysis at ordinary pressure but submitted to hydrazinolysis at higher pressure to form p-nitrophenylhydrazine (VII) and the corresponding aminophenol derivative (VIII), with a minute amount of the reduction product as diamino derivative (IX). Under some reaction conditions, the substance (VIII) further underwent autoreduction to form nitroaniline (VIIb) and nitrobenzene (VIIa).