ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 41, Number 2
JKCSEZ 41(2)
April 20, 1997 

Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at 35.0 ℃ have been carried out in order to elucidate the reaction mechanism. Individual rate constants kXY and kXZ were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett ρx, ρy and ρz values and cross interaction constant ρx, ρy and ρz values. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack SN2 mechanism with four-membered ring transition state from unusually large magnitude of the ρX, ρXY, ρXZ and positive ρY values.