Journal of the American Chemical Society p. 3573 - 3578 (1983)
Update date:2022-08-17
Topics:
Ritchie, Calvin D.
Rate and equilibria constants for the reactions of 3,6-bis(dimethylamino)xanthylium cation with several amines and thiolates in dimethyl sulfoxide solution have been measured.Assumptions used in previous work to estimate equilibrium constants in dimethyl sulfoxide solution are found to be incorrect.Conclusions reached from those assumptions are not supported by the present data, and there are no examples in the present or past work where solvent effects on rates are appreciably greater than those on the corresponding equilibria for simple bond-forming reactions.Equilibrium constants have also been determined for the reactions of thiophenoxide and trifluoroethoxide ions with (p-(dimethylamino)phenyl)tropylium ion in water.The kinetic reactivities of trifluoroethoxide relative to hydroxide ion and of thiophenoxide relative to alkanethiolates are much greater than the corresponding equilibrium reactivities.In addition, an example of a slow, rate-determining, proton transfer in the reaction of morpholine with 3,6-bis(dimethylamino)xanthylium cation in dimethyl sulfoxide has been found.
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