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 N_T scale of solvent nucleophilicity and Y_OTs 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).
Literature values (I. S. Koo, K. Yang, S. K. An, S.-K. Lee, I. Lee, Bull. Korean Chem. Soc. 2000, 21, 1011) for the specific rates of solvolysis of methanesulfonyl chloride have been extended to fluoroalcohol-containing solvents and for 42 solvents at 45.0 °C values are obtained (using N_T and Y_Cl values) of 1.29 for l and of 0.55 for m (R = 0.964).
It is proposed that both substrates solvolyze by an S_N2 pathway.

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