联苯在β-蒎烯光氧化中的电子中继  

Electron Relay of Biphenyl in Photooxygenation of β-Pinene

作　　者：吴国生[1] 陶涛[1] 邱发洋[1] 王银章 

机构地区：[1]中国科学院上海有机化学研究所,上海200032 [2]山西大学化学系

出　　处：《化学学报》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

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）^■之间电子转移而生成的超氧负离子（O₂^■）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).

关 键 词：Β-蒎烯 光氧化 联苯 电子中继 

分 类 号：O624.13[理学—有机化学]