Kinetics and mechanism of the pyridinolysis of phenyl chloroformates in acetonitrile

HJ Koh, KL Han, HW Lee, I Lee

Index: Koh, Han Joong; Han, Kwang Lae; Lee, Hai Whang; Lee, Ikchoon Journal of Organic Chemistry, 1998 , vol. 63, # 26 p. 9834 - 9839

Full Text: HTML

Citation Number: 58

Abstract

Kinetic studies on the reactions of Y-phenyl chloroformates with X-pyridines in acetonitrile are carried out at 25.0° C. Both the Hammett and Brönsted plots are linear with enhanced substituent constants, σp-, and basicities, p K a-, for strong para π-acceptor X-substituents, p- CN and p-CH3CO. This indicates that the electron-rich formate (OCO) moiety overlaps with the pyridine ring π-system enabling, through conjugation with the para π-acceptors, the ...