Acta Chimica Sinica ›› 1983, Vol. 41 ›› Issue (8): 765-768. Previous Articles    

Original Articles

单电子转移反应 I.单电子转移反应引发的碳一氟键异裂--顺-1,2二苯基六氟环丁烷的烷氧基化脱氟取代反应

蒋锡夔;张毓凰;汪大莘;董敏华   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1983-08-15

Electron transfer reactions I: C-F bond cleavage mediated by an electron-transfer process -- alkoxy-defluorination of 1, 2-diphenylhexafluorocyclobutane

JIANG XIKUI;ZHANG YUHUANG;WANG DASHEN;DONG MINHUA   

  • Published:1983-08-15

A novel reaction involving electron transfer and the breakage of a C-F bond has been investigated. In this reactio, 1, 2-diphenylhexafluorocyclobutane(1)reacts with i-PrONa to yield a substitution product 9. The reaction has to be photostimulated, and O2 and p-dinitrobenzene inhibit the reaction. Interestingly and unexpectedly, other alkoxides, viz. MeO-, EtO-, n-PrO- and t-BuO-, do not react with 1. Thus the reaction does not look like a SRN 1. However, the most amazing fact is: only the cis isomer of 1 reacts, whereas the trans isomer does not. Possibly, simultaneous breakage of α-C-H bond (in the i-PrO-) and formation of a (temporary) H-F bond is involved in a very tight transition state of the (caged?) reaction between the radical anion of 1 and the i-PrO.

Key words: HYDROCARBON WITH TWO PHENYLS P, ELECTRON TRANSFER, FLUOROHYDROCARBON, FREE RADICAL REACTION, CYCLOBUTANE P

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