Amidines. IV. : Hydrolysis of N^1-Acyl Derivatives of N^1,N^2-Diarylamidine in Carboxylate Buffer Solution

概要

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In the hydrolysis of N^1-benzoyl-N^1,N^2-diphenylacetamidine (1) in carboxylate buffer solutions, nucleophilic attack of the catalytic acid was proved to take place at the amide carbonyl carbon (pathway d) and presumably also at the amidine central carbon (pathway e) in parallel to the normal hydrolysis processes. Mixed acid anhydride and N^1,N^2-diphenylacetamidine were formed by pathway d, and the former reacted with aniline formed by further hydrolysis of the latter to give two N-acylanilines. In parallel with this process, the mixed anhydride reacts with water to give two carboxylic acids. In this case, carboxylic acid acts as a nucleophilic catalyst.The reaction of 1 and p-methoxybenzoic acid under anhydrous conditions gave products derived from the attack of p-methoxybenzoate ion at both amide carbonyl and amidine central carbons.Hydrolysis of N^1-benzoyl-N-^1,N^2-diphenylformamidine (7) in acetate buffer solution proceeded mainly through the ordinary hydrolysis pathway. Formation of a small amount of acetanilide implies that the reaction proceeds through pathway d or e to a small extent.In hydrolysis of N^1-tosyl-N^1,N^2-di(p-methylphenyl)acetamidine (6b) in glycolate buffer solution, a small amount of N-(acetoxyacetyl)-p-toluidine was formed together with the ordinary hydrolysis products. This implies that the reaction proceeds through pathway e to a small extent.
社団法人日本薬学会の論文
1990-05-25