Kinetics and Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangements of Cis,cis-1,3,5-octatriene

Author

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

Abstract

Thermal isomerizations of cis,cis-1,3,5-octatriene at 60-111°C occur with activation parameters log A = 9.1 and E_a = 21.3 (to cis,cis,cis-2,4,6-octatriene) and E_a = 20.2 kcal mol^-1 (to cis,cis,trans-2,4,6-octatriene). Primary deuterium kinetic isotope effects for these [1,7] sigmatropic shifts are found to be 6.4-7.7 and not markedly temperature dependent, indicative of a linear or nearly linear C7-H-C1 geometry in the transition-state structure.

Recommended Citation

J. E. Baldwin and P. Reddy, "Kinetics and Deuterium Kinetic Isotope Effects for the Thermal [1,7] Sigmatropic Rearrangements of Cis,cis-1,3,5-octatriene," Journal of the American Chemical Society, vol. 109, no. 26, pp. 8051 - 8056, American Chemical Society (ACS), Dec 1987.

The definitive version is available at https://doi.org/10.1021/ja00260a017

Department(s)

Chemistry

International Standard Serial Number (ISSN)

0002-7863

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 1987 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Dec 1987