• Bulletin of the Korean Chemical Society
• /
• v.25 no.8
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• pp.1280-1282
• /
• 2004

• Journal of the Korean Chemical Society
• /
• v.22 no.3
• /
• pp.158-163
• /
• 1978

The four 1,1-disubstituted 2-vinylcyclopropanes, 1,1-diphenyl-2-vinylcyclopropane (1a), 1,1-dicyano-2-vinylcyclopropane(1b), ethyl 1-cyano-2-vinylcyclopropanecarboxylate(1c), and diethyl 2-vinylcyclopropane-1,1-dicarboxylate(1d) rearranged below $300{\circ}C$ to the corresponding 4,4-disubstituted cyclopentenes, 4,4-diphenylcyclopentene(2a), 3-cyclopentene-1,1-dicarboxylate(2d). Diphenpyl derivative 1a rearranged almost quantitatively to 4,4-diphenylcyclopentene(2a) at the temperature of $250{\circ}C$. Although dicyano derivative 1b in solution underwent the thermal rearrangement at rather low temperature of $170{\circ}C$, the other vinylcyclopropanes, 1c and 1d, in solution rearranged thermally above $220{\circ}C$. In the thermal reaction of 1b, 1c, and 1d considerable amounts of polymers 3 were also produced. Also detected product was the ring-opened diene, ethyl 2-cyano-2,4-hexadienoate(4), in case of the pyrolysis of 1c. The observed facile rearrangement of disubstituted vinylcyclopropanes was explained by the radical stabilization effect of substituents on the diradical intermediates 5.