Limits to oxidation of organic substrates. SET oxidative processes of commonly used solvents as revealed through the photochemical reaction with 1,2,4,5-benzenetetracarbonitrile

被引:7
作者
Fagnoni, M
Vanossi, M
Mella, M
Albini, A
机构
[1] Dip. Chimica Organica, 27100 Pavia
关键词
D O I
10.1016/0040-4020(95)01013-0
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The chemical reactivity upon single electron transfer of some common solvents has been explored This has been obtained by using photo excited benzene-1,2,4,5-tetracarbonitrile (TCB) as the oxidant. Under this condition acetonitrile, isobutyronitrile, methanol and trifluoroethanol all undergo alpha-deprotonation from their radical cations giving alkyl radicals which are trapped by TCB- and yield alkylbenzenetricarbonitriles or products derived from them. The reaction of the two aliphatic nitriles occurs only in the presence of protic additives, and is accompanied by a different fragmentation leading to methyl (or respectively isopropyl) radicals. Trifluoroacetic acid decarboxylates, probably via oxidation of the anion. TCB irradiation in neat methanol (rather than in MeOH-MeCN mixtures) leads to protic addition onto the cyano group, finally giving dicyanoindoles.
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页码:1785 / 1796
页数:12
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