Croat. Chem. Acta 69 (1996) 563-568.

Reactivity of Some Tertiary Chlorides with Methoxy and Olefinic Neighboring Group

Stanko Borcic, Olga Kronja, Kresimir Humski and Sandra Miletic

Faculty of Pharmacy and Biochemistry, University of Zagreb,
A. Kovacica 1, P. O. Box 156, 10000 Zagreb, Croatia

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Solvolysis rate of tertiary chlorides 1-6 and their hexadeuterated analogs 1-d6-6-d6 were measured in ethanol (fi=80%) and 2,2,2-trifluoroethanol (W=97%). The beta-deuterium KIE calculated showed that chloride 1solvolyzes with n-participation of the methoxy group in the rate determining step, while chloride 2 solvolyzes mainly by way of a kc process. Based on the reduced beta-deuterium isotope effect, it was also concluded that in the solvolysis of chloride 5 pi-electrons take part in the rate-determining step.