Effect of pressure on the rate of [3,3]-sigmatropic rearrangements

Autor: G. A. Stashina, V. M. Zhulin, G. D. Gamalevich, E. M. Vasil'vitskaya, B. S. El'yanov, Edward P. Serebryakov
Rok vydání: 1986
Předmět:
Zdroj: Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 35:302-306
ISSN: 1573-9171
0568-5230
Popis: 1. It was found that pressure has an accelerating effect on the rearrangement of 3,5-dimethyl-1,5-hexadien-3-ol to 6-methyl-6-hepten-2-one; the volume effect of the activation of this reaction at 180°C, equal to −10 cm3/mole, indicates a concerted reaction mechanism and looseness in the transition state. 2. An equation is proposed which describes the effect of pressure on the rate constants of the Claisen and Cope rearrangements, the parameters of which are consistent with the fact that the cleavage and formation of the bonds takes place simultaneously in the reaction.
Databáze: OpenAIRE
Externí odkaz: