Carbon Acidity. 53. Kinetic and Equilibrium Acidities of Fluorinated Bicycloalkanes

Author

Andrew Streitwieser
David Holtz
Gene R. Ziegler
James O. Stoffer, Missouri University of Science and TechnologyFollow
M. Lee Brokaw
Francois Guibé

Abstract

Base-catalyzed tritium exchange kinetics in methanolic sodium methoxide are reported for lH-4-Y-perfluorobicyclo[2.2.1]heptanes, Y = F (1), H (2), CH3 (3), Br (4), I (5), CF3 (6), 1H-perfluorobicyclo[2.2.2]octane (7), and lH-perfluorobicyclo[2.2.1]hept-2-ene (8). The primary isotope effect for 2 is weak. Equilibrium cesium ion pair acidities are reported for compounds 1,2,3,6,7, and 8 in cyclohexylamine relative to conjugated hydrocarbon indicators. A Brønsted plot of the kinetic and equilibrium acidities has a slope close to unity and is used to assign pK values to related halogenated carbon acids. The acidities of the fluorinated bicycloalkanes can be accommodated completely by a classical field effect as modeled by Kirkwood-Westheimer calculations.

Recommended Citation

A. Streitwieser et al., "Carbon Acidity. 53. Kinetic and Equilibrium Acidities of Fluorinated Bicycloalkanes," Journal of the American Chemical Society, American Chemical Society (ACS), Jan 1976.

The definitive version is available at https://doi.org/10.1021/ja00433a030

Department(s)

Chemistry

International Standard Serial Number (ISSN)

0002-7863

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 1976 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jan 1976