二苯甲酮与醚、酚的光化夺氢反应中产生的活泼自由基的ESR研究

波谱学杂志 ›› 1986, Vol. 3 ›› Issue (2): 165-170.

二苯甲酮与醚、酚的光化夺氢反应中产生的活泼自由基的ESR研究

纪海星, 徐广智

中国科学院化学研究所, 北京

收稿日期:1985-12-25 修回日期:1986-02-01 出版日期:1986-06-05 发布日期:2018-01-23
基金资助:
中国科学院科学基金资助课题

AN ESR STUDY OF ACTIVE RADICALS PRODUCED IN THE PHOTOCHEMICAL HYDROGEN ABSTRACTION REACTIONS BETWEEN ETHERS,PHENOLS AND BENZEOPHENONE

Ji Haixing, Xu Guangzhi

Institute of chemistry, Academia sinica, Beijing

Received:1985-12-25 Revised:1986-02-01 Online:1986-06-05 Published:2018-01-23

摘要/Abstract

摘要： 本文用具立体阻碍的自旋捕捉剂2,4,6,-三-特丁基亚硝基苯(TBN)与ESR相结合的方法,研究了七种醚及四种酚与二苯甲酮光化夺氢反应中产生的活泼自由基。从ESR谱的超精细结构确证,处于激发态的二苯甲酮是夺取醚中接于氧的a-c上的氢;
?₂CO+ROR→?₂?OH+R'?HOR
而且只是其中的R'?HOR可与TBN形成(Ⅰ)型及(Ⅱ)型两种自由基加合物:
对于苯酚衍生物而言,二苯甲酮却是夺取酚羟基中的质子而形成R-O-?,它与TBN也形成(Ⅰ)型及(Ⅱ)型两种自由基加合物。

Abstract: The active radicals produced in the photochemical hydrogen abstraction reactions between benzophenone and ethers or phenols have been studied by combination of sqin trapping reagent 2,4,6-tri-t-butylnitrosobenyene (TEN) by ESR spectroscopy. Results demostratethat benzophenone can abstract hvdrogen from a-c adjacent to oxygen of ethers as follows.
ϕ₂CO+ROR→ϕ₂ĊOH+R'ĊHOR
And the R'ĊHOR reacts with TBN to form either Nitroxide(I) or N-alkoxyanilino spin adducts. For the case of phenols, benzophenone abstracts hydrogen from phenolic hydroxyl of phenols to from phenoxy radicals (R-O-Ȯ). They also react with TEN to formeither(I) or (Ⅱ) spin adducts.

纪海星, 徐广智. 二苯甲酮与醚、酚的光化夺氢反应中产生的活泼自由基的ESR研究[J]. 波谱学杂志, 1986, 3(2): 165-170.

Ji Haixing, Xu Guangzhi. AN ESR STUDY OF ACTIVE RADICALS PRODUCED IN THE PHOTOCHEMICAL HYDROGEN ABSTRACTION REACTIONS BETWEEN ETHERS,PHENOLS AND BENZEOPHENONE[J]. Chinese Journal of Magnetic Resonance, 1986, 3(2): 165-170.