Chemical and Pharmaceutical Bulletin
Online ISSN : 1347-5223
Print ISSN : 0009-2363
ISSN-L : 0009-2363
Amidines. VII. : Hydrolysis and Alcoholysis of Carboxamides under Mild Conditions
Machiko ONOIchiro ARAYAReiko TODOROKIShinzo TAMURA
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1990 Volume 38 Issue 7 Pages 1824-1831

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Abstract

Hydrolysis and alcoholysis of carboxamides derived from primary aliphatic amines were achieved under mild conditions. Amide exchange reaction between carboxamides and N1-acyl-N1, N2-di (p-nitrophenyl) formamidines (1) gave N1-acyl-N1-alkyl-N2-(p-nitrophenyl)formamidines (2) which were readily hydrolyzed or alcoholyzed to give N1-alkyl-N2-(p-nitrophenyl)formamidines (4) and carboxylic acid or its ester. Compounds 4 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 1 and N-acyl derivatives of amino alcohols was quite complex. Alcoholysis of N-ethyl-N, N'-ethylenebis (p-chlorobenzamide) (8a) by this method gave N-(2-aminoethyl)-N-ethyl-p-chlorobenzamide (8b). Thus, the selective alcoholysis of diacyl derivative of diamines, which contain primary and secondary amino groups, was achieved.

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© The Pharmaceutical Society of Japan
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