Solvolysis of 1-aryl-2, 2, 2-trifluoroethyl sulfonates. Kinetic and stereochemical effects in the generation of highly electron-deficient carbocations

AD Allen, IC Ambidge, C Che, H Micheal…

Index: Allen, Annette D.; Ambidge, I. Christopher; Che, Claudius; Micheal, Hany; Muir, Ronald J.; Tidwell, Thomas T. Journal of the American Chemical Society, 1983 , vol. 105, # 8 p. 2343 - 2350

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Citation Number: 51

Abstract

Abstract: Solvolysis rates of sulfonates XC6H4CH (03SR) CF3 (R= p-To1 or CF,) correlate with u'(X) with values of p+ between-6.7 and-1 1.9 depending upon solvent. For the tosylates the rates depend on the solvent parameter YoTs with values of l? lOTs of 0.76 (X= p-MeO), 0.94 (X= p-Me), and 0.69 (X= H). These results are interpreted in terms of rate-limiting carbocation formation (the kc process). Rates for PhCH (OTf) CF3 (12e) in ten solvents ...