Kinetics and deuterium kinetic isotope effects for the thermal [1, 7] sigmatropic rearrangements of cis, cis-1, 3, 5-octatriene

JE Baldwin, VP Reddy

Index: Baldwin, John E.; Reddy, V. Prakash Journal of the American Chemical Society, 1987 , vol. 109, # 26 p. 8051 - 8056

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Citation Number: 22

Abstract

Abstract: Thermal isomerizations of cis, cis-1, 3, 5-octatriene at 60-1 11 “C occur with activation parameters log A= 9.1 and E,= 21.3 (to cis, cis, cis-2, 4, 6-octatriene) and E,= 20.2 kcal mol-l (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-Cl geometry in the transition-state ...