MECHANISM AND SOLVENT REORGANIZATION ACCOMPANYING HYDROLYSES OF ANCHIMERICALLY ASSISTED ALKYL HALIDES IN WATER

This paper deals with the problem of solvent reorganization, anchimeric assistance, and mechanism for hydrolysis of nine alkyl halides where the neighboring group is -OH, -OMe, or -SMe. By using the temperature coefficient of the enthalpy ([formula-omitted]) as a gauge of relative solvent reorganization, we show that the transition state in the hydrolysis of those alkyl halides giving evidence of anchimeric assistance resembles that for an Sn1 mechanism. This conclusion was supported in one case by 13C labeling experiments in spite of product analysis seemingly favoring Sn2 nucleophilic displacement by the solvent. © 1969, American Chemical Society. All rights reserved.