695-90-9Relevant academic research and scientific papers
Cleavage vs Rearrangement Ratios and Secondary Deuterium Kinetic Isotope Effects in the Thermolysis of Conformationally Fixed Cisoid Vinylcyclobutanes
Gajewski, Joseph J.,Paul, Gitendra
, p. 1986 - 1989 (2007/10/02)
The first-order rate constants for the thermally induced retro 2+2 cleavage and rearrangement of 5-methylenespirononane occur in a 1:2 ratio.In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes.Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted.For the rearrangement of 5-methylenespirooctane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (kH/kD2) is 1.086 +/- 0.023.This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate.The secondary KIE for cleavage of 5-methylenespirooctane is 1.025 +/- 0.027.
The Disproportionation of cis-Bicyclonona-3,7-diene Catalyzed by Fe(CO)5 and Cp2Fe2(CO)4
Kagayama, Takashi,Okabayashi, Shinji,Amaike, Yoichi,Matsukawa, Yasuo,Ishii, Yasutaka,Ogawa, Masaya
, p. 2297 - 2298 (2007/10/02)
cis-Bicyclonona-3,7-diene (1) was catalytically disproportionated by the use of Fe(CO)5 and Cp2Fe2(CO)4 to bicyclonon-1(6)-ene (3) and indan (4).However, the same reaction catalyzed by the use of other metal carbonyls gave merely small amount of 3 and 4, while those using Pd- and Rh-carbons yielded only 4 and the starting material, 1, respectively.
The 9-Decalyl and Related Cations. VI Solvolysis of Pent-4-enyl p-Nitrobenzenesulfonate in 1,1,1,3,3,3-Hexafluoropropan-2-ol and of 3-(Cyclohex-1'-enyl)propyl p-Nitrobenzenosulfonate in 2,2,2-Trifluoroethanol and 1,1,1,3,3,3-Hexafluoropropan-2-ol
Ferber, Peter H.,Gream, George E.
, p. 1051 - 1061 (2007/10/02)
Kinetic and product studies have established that pent-4-enyl p-nitrobenzenesulfonate undergoes insignificant solvolysis (1.5percent) by the ?-route in 1,1,1,3,3,3-hexafluoropropan-2-ol. ?-Participation to give the perhydroinden-3a-yl (8-hydrindyl)cation during the solvolysis of 3-(cyclohex-1'-enyl)propyl p-nitrobenzenesulfonate, a substituted pent-4-enyl derivative, in fluorinated alcohols is, however, significant.In buffered 2,2,2-trifluoroethanol, it occurs to the extent of 30percent; in buffered and unbuffered 1,1,1,3,3,3-hexafluoropropan-2-ol, the values are 96 and 98percent, respectively.
