Abstract

Electrophilic amination of methyl N-(hydroxyphenyl)carbamates and methyl N-(4-methoxyphenyl)carbamate with sodium azide in 86% polyphosphoric acid (PPA) at 55–60°C regioselectively afforded methyl N-(3-amino-2-hydroxyphenyl)-, N-(4-amino-3-hydroxyphenyl)-, N-(3-amino-4-hydroxyphenyl)-, and N-(3-amino-4-methoxyphenyl)carbamates, i.e., the amino group entered the ortho position with respect to the hydroxy or methoxy group. The reactions of methyl N-(4-methoxyphenyl)carbamate with nitromethane and nitroethane in 80% PPA at 95–110°C gave methyl N-(3-carbamoyl-4-methoxyphenyl)carbamate and methyl N-(3-acetamido-4-methoxyphenyl)carbamate, respectively. Methyl N-[4-(N′-hydroxyethanimidamido)phenyl]carbamate was obtained by reaction of 4-[(methoxycarbonyl)amino]benzoic acid with excess nitroethane in 86% PPA at 125°C.

中文翻译：

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多磷酸中取代的氨基甲酸酯的胺化，酰胺化和酰胺化

摘要

N-（羟苯基）氨基甲酸甲酯和N-（4-甲氧基苯基）氨基甲酸甲酯与叠氮化钠在86％的多磷酸（PPA）中在55–60°C时进行亲电胺选择性选择性生成N-（3-氨基-2-羟苯基） ）-，N-（4-氨基-3-羟基苯基）-，N-（3-氨基-4-羟基苯基）-和N-（3-氨基-4-甲氧基苯基）氨基甲酸酯，即氨基进入相对于羟基或甲氧基的邻位。甲基的反应中ñ -氨基甲酸叔丁酯与硝基甲烷和硝基乙烷中的80％PPA在95-110℃（4-甲氧基苯基），得到甲基ñ - （3-氨基甲酰基-4-甲氧基苯基）氨基甲酸叔丁酯和甲基Ñ-（3-乙酰氨基-4-甲氧基苯基）氨基甲酸酯。甲基Ñ [4-（ - ñ在125以86％的PPA [（甲氧基羰基）氨基]苯甲酸用过量硝基乙烷酸°C -通过4反应得到'-hydroxyethanimidamido）苯基]氨基甲酸叔丁酯。