The Journal of organic chemistry

Aminolysis of aryl chlorothionoformates with anilines in acetonitrile: Effects of amine nature and solvent on the mechanism

HK Oh, JS Ha, DD Sung, I Lee

Index: Oh, Hyuck Keun; Ha, Joo Suk; Sung, Dae Dong; Lee, Ikchoon Journal of Organic Chemistry, 2004 , vol. 69, # 24 p. 8219 - 8223

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Citation Number: 35

Abstract

The aminolysis of aryl chlorothionoformates (7, YC6H4OC (S) Cl) with anilines (XC6H4NH2) in acetonitrile at 5.0° C has been investigated. The rates are slower than those for the corresponding reactions of aryl chloroformates (6, YC6H4OC (O) Cl). This rate sequence is a reverse of that for alkyl chloroformates (1-4) in water, for which rate-limiting formation of a tetrahedral intermediate, T±, is predicted. On the basis of the large negative cross- ...