31845-13-3Relevant academic research and scientific papers
On the Mechanism of the Thermal Rearrangement of Bicyclohexane: Dispirohexane-3',1''-cyclopropane> and Analogously Substituted Derivatives as New Model Compounds
Kaufmann, Dieter,Meijere, Armin de
, p. 3134 - 3150 (2007/10/02)
Upon thermolysis the 2,3-diazabicyclooct-2-enes 10a-c yield only the thermodynamically more stable 1,5-hexadienes, namely 11, 13, and 15, respectively.Upon photolysis, however, remarkable proportions of the new bicyclohexane derivatives 2 (66percent), 4 (29percent), and 3 (58percent), respectively, are formed besides the hexadienes; the by-product (2percent) from 10a most probably is the hexalin 12, as it would arise from an intermediate diradical by neighboring group participation of both three-membered rings.The thermolyses of 2, 3, and 4 follow first order rate laws and yield 11, 13, and 15.According to the kinetic data, which best fit a two-step mechanism, the diradical from 2 is stabilized purely electronically by 25.8 kJ/mol with respect to the diradical from 4.
