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化学学报
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化学学报 ›› 1992, Vol. 50 ›› Issue (4): 383-390. 上一篇    下一篇

研究论文

联苯在β-蒎烯光氧化中的电子中继

吴国生;陶涛;邱发洋;王银章   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1992-04-15

Electron relay of biphenyl in photooxygenation of β-Pinene

WU GUOSHENG;TAO TAO;QIU FAYANG;WANG YINZHANG   

  • Published:1992-04-15

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被引次数

6 | 1

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(O^-~2)复合。

关键词: 光化学反应, 计算, 光氧化, 敏化, 蒎烯, 联苯, MNDO法, 桃金娘烯醇, 电子中继

Long-time photooxygenation of b-pinene (I) with singlet oxygen leads to a mass product distribution. The yield of myrtenol (II) is a little improved by electron-transfer photooxygenation with dicyanoanthracene (DCA), but is almost double by the addition of biphenyl as cosensitizer. Competitive electron transfer of biphenyl to DCA over I has been proved to stem from higher HOMO of biphenyl by means of MNDO calculation Biphenyl radical cation gets one electron back from I to recycle biphenyl and form I radical cation, which combines with superoxide ion generated from electron transfer between ground oxygen and (DCA)-.

Key words: PHOTOCHEMICAL REACTION, CALCULATION, PHOTOOXIDATION, SENSITIZATION, PINENE, XENENE, MNDO METHOD, MYRTENOL

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