Title

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

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 AH = 9.8 and EaH = 21.5 kcal/mol. Parallel kinetic work with the 7-deuterio-7-methyloctatriene establishes the Arrhenius parameters log AD = 10.3 and EaD = 23.5 kcal/mol. Thus AD/AH = 3.2 and (EaD - EaH) = 2.0 kcal/mol, and a substantial tunneling component for the [1,7] sigmatropic hydrogen migration is evident. © 1988 American Chemical Society.

Department(s)

Chemistry

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

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


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