Absolute rate constants for iminyl radical reactions

被引:65
作者
LeTadicBiadatti, MH
CallierDublanchet, AC
Horner, JH
QuicletSire, B
Zard, SZ
Newcomb, M
机构
[1] ECOLE POLYTECH,CNRS,ORGAN SYNTH LAB,F-91128 PALAISEAU,FRANCE
[2] WAYNE STATE UNIV,DEPT CHEM,DETROIT,MI 48202
[3] CNRS,INST CHIM SUBST NAT,F-91198 GIF SUR YVETTE,FRANCE
关键词
D O I
10.1021/jo961530+
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The kinetics of cyclization of the 2-methyl-6,6-diphenyl-5-hexeniminyl radical (3) were measured by laser flash photolysis methods from 0 to 50 degrees C, and the kinetics of trapping of radical 3 by thiophenol and p-chlorothiophenol were determined between 4 and 83 degrees C by indirect methods using the unimolecular rate constants as the basis values. Radical 3 cyclizes with a rate constant of 2.2 x 10(6) s(-1) at 25 degrees C and reacts with thiophenol and p-chlorothiophenol at this temperature with rate constants of 0.6 and 1.4 x 10(7) M(-1) s(-1), respectively. Bu(3)SnH reacted with 3 too slowly to prevent nearly complete cyclization, but a crude rate constant for the trapping reaction was estimated. The cyclization and trapping reactions of iminyl radical 3 are slower than the corresponding reactions of alkyl radicals.
引用
收藏
页码:559 / 563
页数:5
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