Correlation of the rates of solvolysis of (arylmethyl)methylphenyl-sulfonium ions

• Published in: Journal of the Chemical Society. Perkin Transactions 2
• Main Author: Kevill D.N.; Ismail N.H.J.
• Format: Article
• Language: English
• Published: Royal Society of Chemistry 1998
• Online Access: https://www.scopus.com/inward/record.uri?eid=2-s2.0-0040560233&doi=10.1039%2fa803859g&partnerID=40&md5=d1b81494c412a3e2610472b8670dcf3d

The specific rates of solvolysis of the benzylmethylphenylsulfonium ion (prepared as the trifluoromethanesulfonate salt) and five benzylic ring-substituted derivatives can be satisfactorily correlated using NT solvent nucleophilicity values. Addition of a secondary term, governed by the aromatic ring parameter (I), shows the sensitivities towards changes in this parameter to fall and those towards changes in NT to rise with increasing electron-withdrawing ability of the substituent. The Hammett ρ values with electron-withdrawing substituents (based on ρ+ values) vary from -0.9 in 95% acetone to -1.8 in 97% 2,2,2-trifluoroethanol. These Grunwald-Winstein and Hammett analyses are compared to those previously reported, with essentially the same solvents and substituents, for solvolyses of arylmethyl p-toluenesulfonates.