Primary Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangement of 7-methylocta-1,3(Z),5(Z)-triene

Author

John E. Baldwin
Prakash Reddy, Missouri University of Science and TechnologyFollow

Abstract

7-Methylocta-1,3(Z),5(Z)-triene isomerizes to 2-methylocta-2,4(Z),6(Z)-triene over the temperature range 60-115 °C through a first-order process characterized kinetically by the activation parameters log A^H = 9.8 and E_a^H = 21.5 kcal/mol. Parallel kinetic work with the 7-deuterio-7-methyloctatriene establishes the Arrhenius parameters log A^D = 10.3 and E_a^D = 23.5 kcal/mol. Thus A^D/A^H = 3.2 and (E_a^D - E_a^H) = 2.0 kcal/mol, and a substantial tunneling component for the [1,7] sigmatropic hydrogen migration is evident.

Recommended Citation

J. E. Baldwin and P. Reddy, "Primary Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangement of 7-methylocta-1,3(Z),5(Z)-triene," Journal of the American Chemical Society, vol. 110, no. 24, pp. 8223 - 8228, American Chemical Society (ACS), Nov 1988.

The definitive version is available at https://doi.org/10.1021/ja00232a040

Department(s)

Chemistry

International Standard Serial Number (ISSN)

0002-7863

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 1988 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Nov 1988