Rate and Product Studies with Methanesulfonic Anhydride Under Solvolytic Conditions and a Comparison with Methanesulfonyl Chloride Solvolysis
|Dennis N. Kevill 1, Zoon Ha Ryu 2, Malcolm J. D Souza 3, Lamia Yaakoubd 3, Fumie Koyoshi 3|
1. Northern Illinois University, Dekalb, Illinois 60115-2862, United States
The specific rates of solvolysis of methanesulfonic anhydride have been measured conductometrically at -10 °C in 41 solvents. Use of the extended Grunwald-Winstein equation (with the NT scale of solvent nucleophilicity and YOTs scale of solvent ionizing power) leads to an l value of 0.95 and an m value of 0.61 with a multiple correlation coefficient (R) of 0.973. Selectivity values in binary hydroxylic solvents favor alcohol attack in EtOH-H2O (S value of 1.2 in 90% EtOH rising to 4.0 in 40% EtOH) and in MeOH-H2O (S value of 3.7 in 90% MeOH rising to 6.0 in 50% MeOH). In 2,2,2-trifluoroethanol-H2O, S values are much lower (at about 0.1). Entropy of activation values are appreciably negative (-12 to -34 cal mol-1 K-1).
Presentation: oral at 18th Conference on Physical Organic Chemistry, Symposium 2, by Dennis N. Kevill
See On-line Journal of 18th Conference on Physical Organic Chemistry
Submitted: 2006-05-09 18:48 Revised: 2009-06-07 00:44
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