Amidines. VII. Hydrolysis and alcoholysis of carboxamides under mild conditions.

Abstract

Amide exchange reaction between carboxamides and N 1 -acyl-N 1 ,N 2 -di(p-nitrophenyl)formamidines (I) gave N 1 -acyl-N 1 -alkyl-N 2 -(p-nitrophenyl)formamidines which were readily hydrolyzed or alcoholyzed to give N 1 -alkyl-N 2 -(p-nitrophenyl)formamidines (II) and carboxylic acid or its ester. Compounds II were hydrolyzed to give aliphatic amine and N-formyl-p-nitroaniline in the presence of acetic acid or hydrochloric acid at room temperature. For the alcoholysis of N-acyl derivatives of amino alcohols, protection of the hydroxyl substituent by an acyl group was essential because the reaction of I and N-acyl derivatives of amino alcohols was quite complex. Alcoholysis of N-ethyl-N,N'-ethylenebis(p-chlorobenzamide) by this method gave N-(2-aminoethyl)-N-ethyl-p-chlorobenzamide. Thus, the selective alcoholysis of diacyl derivative of diamines, which contain primary and secondary amino groups, was achieved