HYDROLYSIS OF PEPTIDE BONDS BY INTRAMOLECULAR PARTICIPATION OF BENZIMIDAZOLIUM IONS

被引：8
作者：
KIRK, KL
COHEN, LA
机构：
[1] Laboratory of Chemistry, National Institute of Arthritis and Metabolic Diseases, National Institutes of Health, Maryland 20014, Bethesda
来源：
JOURNAL OF ORGANIC CHEMISTRY | 1969年 / 34卷 / 02期
关键词：
D O I：
10.1021/jo01254a028
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A series of 5,7-dinitrobenzimidazolyl-4 peptides have been prepared and the rates of hydrolysis of the peptide bond determined as a function of acidity and temperature. It is demonstrated that the rate of hydrolysis is dependent on the degree of protonation of a benzimidazole nitrogen atom. The effectiveness of the intramolecular participation varies with the nature of the peptide side chain and with the degree of alkylation of the imidazole ring. No correlation is observed between pKa and specific rate constant for the various substrates. Heats of ionization and activation parameters are reported for two cases. The compound, 1,2-dimethyl-5,7-dinitrobenzimidazolyl-4-alanylglycine, was found to hydrolyze 65,000 times as rapidly as 2,4-dinitrophenylalanylglycine. © 1969, American Chemical Society. All rights reserved.
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页码：390 / &
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