论文信息 - The Pressure Effect on the 1,5-Sigmatropic Hydrogen Shift of Tropylidene Derivative, 3,3-Diphenyl-3,3a-dihydrocyclohepta[b]furan-2-one

The Pressure Effect on the 1,5-Sigmatropic Hydrogen Shift of Tropylidene Derivative, 3,3-Diphenyl-3,3a-dihydrocyclohepta[b]furan-2-one

The 1,5-sigmatropy of 3,3-diphenyl-3,3a-dihydrocyclohepta[b]furan-2-one was examined in dibutyl ether to 1600 bar at 130 °C. The rearrangement was slightly accelerated with pressure, and was different to the pressure effect of 1,5-sigmatropy of cyclopentadienes. The activation volume was in the range of the concerted process, but its transition state was as loose as those biradical-like.

S. Sugiyama | H. Takeshita

[1] K. Houk,et al. Nature of the migrating group in 1,5-sigmatropic hydrogen shifts , 1985 .

[2] W. L. Noble,et al. Effect of pressure on the rates of sigmatropic shifts. Volume as an indication of a wide mechanistic range , 1983 .

[3] W. L. Noble,et al. Kinetics of reactions in solutions under pressure. 52. Effect of pressure on concerted and stepwise sigmatropic shifts , 1978 .

[4] C. Jutz,et al. Über die cycloaddition von diphenylketen an tropon , 1966 .

[5] C. Walling,et al. Organic Reactions under High Pressure. VI. Some Claisen and Cope Rearrangements , 1962 .

[6] K. Brower. The Volume Change of Activation in the Claisen and Curtius Rearrangements , 1961 .