Diphenyl Etherを基核とするAcid Hydrazide誘導体の合成研究 (第13報)

Diphenyl Ether誘導体のHydrazine Hydrateによる開裂反応 その7

抄録

Hydrazinolysis of mononitro-monomethoxydiphenyl ether, having one nitro and methoxyl on each of the two benzene rings, with hydrazine hydrate was examined. Irrespective of the position of the methoxyl group, compounds (I) with nitro group in the position para to the phenoxyl underwent cleave of the ether-oxygen forming the diphenyl ether to form 4-nitrophenylhydrazine (II) and the corresponding hydroxyanisole derivative (III). Application of higher pressure effected acceleration of this hydrazinolysis and a small amount of 4-amino-methoxydiphenyl ether derivative (V) was obtained besides (II) and (III) (cf. Chart 1).
The compound (VI) with nitro group in the position meta to the phenoxyl failed to undergo hydrazinolysis, either at ordinary or higher pressure, and only the reduction of nitro group occurred to form 3-amino-methoxydiphenyl ether derivative (VII) and a small amount of a reduction product (VIII) or (IX) (cf. Chart 2).
The compound (X) with the nitro group in the position ortho to the phenoxyl easily underwent hydrazinolysis at ordinary pressure to form 2-nitrophenylhydrazine (XI) and the corresponding hydroxyanisole derivative (III). Hydration reaction proceeded with (XI) and 1-hydroxybenzotriazole (XIa) was obtained (cf. Chart 3).