摘要
β-蒎烯的长时间单重态氧光氧化导致复杂的产物分布。二氰基蒽（DCA）敏化的电子转移光氧化使桃金娘烯醇的产率略有改善,但是,添加联苯作共敏化剂使产率几乎翻了一番。在向DCA的竞争性单电子转移中,联苯超过了β-蒎烯。MNDO计算证实其原因是联苯的HOMO较高。联苯正离子游离基从β-蒎烯回收一个电子,再生联苯和生成β-蒎烯正离子游离基,它再与经基态氧与（DCA）<sup>■</sup>之间电子转移而生成的超氧负离子（O<sub>2</sub><sup>■</sup>）复合。
Long-time photooxygenation of β-pinene (2) with singlet oxygen leads to a mass product distribution. The yield of myrteno] (1) is a hittle improved by electron-transfer photooxygenation with dicyanoanthrancene (DCA), but is almost double by the addition of biphenyl as eosensitizer. Competitive electron transfer of biphenyl to DCA over 2 has been proved to stem from higher HOMO of biphenyl by means of MNDO calculation. Biphenyl radical cation gets one electron back from 2 to recycle biphenyI and form 2 radical cation, which combines with superoxide ion generated from electron transfer between ground oxygen and (DCA).
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1992年第4期383-390,共8页
Acta Chimica Sinica
基金
国家自然科学基金资助的课题
