Solvolysis rates of sulfonates XC6H4CH(03SR)CF3 (R = p-Tol or CF3) correlate with +( ) with values of p+ between -6.7 and -11.9 depending upon solvent. For the tosylates the rates depend on the solvent parameter F0Ts with values of Wqts 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 gave a scattered correlation with F0Ts> and optically active 12e reacted with racemization in TFÁ and HFIP and significant inversion in EtOH and AcOH.These results indicate that nucleophilic solvent participation becomes important with this derivative in the more nucleophilic solvents. Deuterium isotope effects for PhCD(OTf)CF3 are not a definitive criterion of mechanism but are consistent with this interpretation.The reactivity of 1 -aryl-1 -methyl-2,2,2-trifluoroethyl tosylates (I) has been investigated by ourselves1 and by (1) (a)

Für die Solvolyse derTosylate (Ia) in einer Reihe von Lösungsmitteln wie z.B. TFA, 97%igem 2,2,2‐ Trifluor‐ethanol oder 97%igem 1,1,1,3,3,3‐Hexafluor‐isopropanol ergeben sich lineare 24 Abhängigkeiten des Logarithmus der Reaktionsgeschwindigkeiten von den Hammett‐ Konstanten o′ und von den Ionisierungsparametern Yder Lösungsmittel.