NEW INSIGHT ON AN OLD REACTION
anhydride concentrations on the order of 10ꢁ4 mol•dmꢁ3, so
catalysis is not an issue with their work. Since the importance of
general base catalysis in ester and anhydride hydrolyses is com-
mon knowledge,[27,28] it seems odd that general base catalysis
has not always been addressed where appropriate. Many of the
anomalies and inconsistencies in the literature, particularly work
involving higher concentrations of anhydride (e.g. Wilsdon,
Sidgwick,[29] Asprey, Wojciechowski, Rice, and Dorcas,[12] and Haji,
Erkey[11]) may be traced to a failure to account for this feature.
Finally, this work sheds some light on aw, which is the third
term on the right-hand side of Eqn (19). Based upon oxygen-18
exchange studies in 60% dioxane/water, Bunton, Fuller, Perry,
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ꢃ
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Follow-on work
While Robertson, Rossall, and Redmond[16] measured the water/
deuterium oxide kinetic solvent isotope effects for the water
hydrolysis of acetic anhydride, studies need to be extended to
determine the effects for the acetate-catalyzed hydrolysis. Proton
inventory analyses for both reaction pathways would be beneficial
for quantifying the number and types of protons involved in the
transition structures. Robertson, Rossall, and Redmond[16] and
Robertson and Rossall[22] also conducted extensive studies on the
hydrolyses of other anhydrides, and estimated rather large nega-
tive activation heat capacities for some of these reactions. In light
of the results from this work, the same type of studies presented
here need to be extended to these other anhydrides to establish
new baselines for these hydrolyses reactions.
[31] M. L. Bender, H. A. Heck, J. Am. Chem. Soc., 1967, 89, 1211.
J. Phys. Org. Chem. (2012)
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