157-33-5Relevant articles and documents
Frey,Stevens
, p. 90,92 (1965)
Wiberg,Lavanish
, p. 365 (1966)
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Wiberg,Lampman
, p. 2173 (1963)
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Smith et al.
, p. 659 (1965)
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Chemical Activation as a Probe of Reaction Mechanism. Synthesis and Thermal Decomposition of 2,3-Diazabicyclohex-2-enes
Chang, Moon Ho,Jain, Rakesh,Dougherty, Dennis A.
, p. 4211 - 4217 (1984)
Gas-phase thermolysis of 2,3-diazabicyclohex-2-ene (1) produces highly vibrationally excited (chemically activated) bicyclobutane (2).The excited 2 rearranges to butadiene, in competition with collisional deactivation by a bath gas.Quantitative modeling using RRKM theory and a stepladder model for collisional deactivation indicates that, of the substantial amount of excess energy available to the products of thermolysis of 1, the great majority lies in the hydrocarbon fragment (2).Within the framework of a mechanistic criterion developed previously by Bauer, this result suggests that 1 decomposes by a stepwise, one-bond cleavage involving an intermediate diazenyl diradical.The synthetic approach to structures such as 1 is developed, as are certain other aspects of the chemistry of 1 and its dimethyl derivative 7.
Bicyclopentanone. Synthesis, Thermal Chemistry, and Photochemistry
Sponsler, Michael B.,Dougherty, Dennis A.
, p. 4978 - 4984 (2007/10/02)
Bicyclopentanone (1) has been prepared in two steps, the key reaction being the ozonolysis of 2-phenylbicyclopentan-2-ol (6).On heating, 1 undergoes cycloreversion to allylketene (13).The activation parameters and solvent effects for this process suggest that the reaction is concerted and that the transition state is relatively nonpolar.The predominant photochemical pathway for 1 is decarbonylation to bicyclobutane (16).Cycloreversion to 13 is a minor reaction mode.Both the thermal and photochemical results are rationalized by considering the high strain energy and novel geometrical features of 1, and, in the latter case, the unusually high energy of its 1(n?excit.) state.
