MECHANISM OF AN INTRAMOLECULAR ADDITION ELIMINATION BETWEEN AMINO AND AMIDE GROUPS - A BIPHASIC BRONSTED PLOT FOR ACID CATALYSIS AS EVIDENCE FOR RATE-LIMITING PROTON-TRANSFER TO THE ADDITION INTERMEDIATE

被引：2

作者：

BAYNHAM, AS ^{[1
]}

HIBBERT, F ^{[1
]}

MALANA, MA ^{[1
]}

机构：

[1] KINGS COLL LONDON,DEPT CHEM,LONDON WC2R 2LS,ENGLAND

来源：

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS | 1992年 / 16期

关键词：

D O I：

10.1039/c39920001110

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Formation of 2-trifluoromethylperimidine from 1-amino-8-trifluoroacetylaminonaphthalene involves intramolecular nucleophilic addition of the amino group to the amide carbonyl followed by elimination to form the cyclic imine; a biphasic Bronsted plot with slopes-alpha ca. 0 and 1.0 respectively for catalysis by acids (HA) with pK(HA) values below and above a break point at pK(HA) 8.5 is compatible with rate-limiting protonation of the zwitterionic addition intermediate by general acids and with a proton switch mechanism for reaction with water.

引用

页码：1110 / 1112

页数：3

共 10 条

[1] NUCLEOPHILIC-ADDITION TO OLEFINS .12. SOLVENT-INDUCED CHANGE IN THE RATE-LIMITING STEP OF THE HYDROLYSIS OF BENZYLIDENEMALONONITRILE IN ACIDIC ME2SO-WATER SOLUTION [J].