Alkene Reactivities in Trifluoroacetic Acid. A Comparison of Norbornene and Protoadamantene in Trifluoroacetic Acid and Aqueous Acid

DOI: 10.1021/ja00375a034

Source and publish data:

Journal of the American Chemical Society p. 3145 - 3149 (1982)

Update date:2022-08-28

Topics:

Authors:

Allen, Annette D.

Tidwell, Thomas T.

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Article abstract of DOI:10.1021/ja00375a034

The kinetics of the reaction of protoadamantene (1) and norbornene (2) in H2SO4, HClO4, and CF3CO2H have been measured and the two alkenes are found to have similar relative reactivities, rate dependencies on acidity, solvent isotope effects, and activation parameters, independent of the particular acid.The reactivity of 2-fluoropropene (7) in H2SO4 has been measured and compared to the reactivity in CF3CO2H.A general correlation of the reactivity of alkenes in CF3CO2H and in aqueous acids is observed.These results are interpreted in terms of rate-determining proton transfer (the Ad_E2 mechanism) for all of the alkenes in aqueous acids and in CF3CO2H.No evidence for the intervention for ? complexes as kinetically significant intermediates was obtained.This is contrary to a reported interpretation of the reaction of 1 in CF3CO2H.