Primary deuterium kinetic isotope effects for the thermal [1, 7] sigmatropic rearrangement of 7-methylocta-1, 3 (Z), 5 (Z)-triene
JE Baldwin, VP Reddy
Index: Baldwin, John E.; Prakash Reddy, V. Journal of the American Chemical Society, 1988 , vol. 110, # 24 p. 8223 - 8228
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Citation Number: 21
Abstract
OC 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.
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