TY - JOUR
T1 - Novel Photoreactions of Benzhydrylidenequadricyclane and Quadricyclanone
T2 - A New Route to Trimethylenemethane and Oxyallyl Derivatives
AU - Hirano, Takashi
AU - Kumagai, Tsutomu
AU - Miyashi, Tsutomu
AU - Akiyama, Kimio
AU - Ikegami, Yusaku
PY - 1991/3/1
Y1 - 1991/3/1
N2 - The irradiation of 3-benzhydrylidenequadricyclane (1) generated a trimethylenemethane (TMM) derivative, 3-benzhydrylidenebicyclo[3.2.0]hept-6-ene-2,4-diyl (3), which dimerized and could be chemically captured by molecular oxygen and acrylonitrile, but not by furan, methanol, or ethyl vinyl ether. The triplet nature of 3 was confirmed by EPR, emission, and absorption spectra. By contrast, the irradiation of quadricyclanone (2) generated the singlet oxyallyl (OA), 3-oxobicyclo[3.2.0]hept-6-ene-2,4-diyl (4), which could be captured by furan, methanol, and ethyl vinyl ether, but not by molecular oxygen or acrylonitrile, indicating the zwitterionic and electron-accepting nature of 4.
AB - The irradiation of 3-benzhydrylidenequadricyclane (1) generated a trimethylenemethane (TMM) derivative, 3-benzhydrylidenebicyclo[3.2.0]hept-6-ene-2,4-diyl (3), which dimerized and could be chemically captured by molecular oxygen and acrylonitrile, but not by furan, methanol, or ethyl vinyl ether. The triplet nature of 3 was confirmed by EPR, emission, and absorption spectra. By contrast, the irradiation of quadricyclanone (2) generated the singlet oxyallyl (OA), 3-oxobicyclo[3.2.0]hept-6-ene-2,4-diyl (4), which could be captured by furan, methanol, and ethyl vinyl ether, but not by molecular oxygen or acrylonitrile, indicating the zwitterionic and electron-accepting nature of 4.
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U2 - 10.1021/jo00005a044
DO - 10.1021/jo00005a044
M3 - Article
AN - SCOPUS:0000640772
SN - 0022-3263
VL - 56
SP - 1907
EP - 1914
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 5
ER -