alpha-Thioxothioamides [4+2] and [2+2] cycloaddition reactions with aryl isothiocyanates and phenyl isocyanate

被引:0
|
作者
Marchand, E [1 ]
Morel, G [1 ]
机构
[1] UNIV RENNES 1,LAB SYNTH & ELECTROSYNTH ORGAN,UMR 6510,F-35042 RENNES,FRANCE
来源
BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE | 1997年 / 134卷 / 06期
关键词
1,4-dithiabutadiene; 4-aza-1-thiabutadiene; isothiocyanate; ring contraction by sulfur extrusion; 2-thioxothiazole; 2-iminothiazole;
D O I
暂无
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Aryl and methyl isothiocyanates react with 1,2-dithiocarbonyl compounds 2 to give a mixture of 2,3-dihydro-2-thioxothiazole 3 and 2-iminothiazole 5. The product ratios depend mainly on the nature of the starting (RNCS)-N-1. We show that alpha-iminothioamides 4 are intermediates in the formation of cycloadducts 5. The results are explained by [4+2] and [2+2] additions to the C=N bond of the heterocumulene followed by ring contraction of the 2,3-dihydro-1,4,2-dithiazine 6 (sulfur extrusion) or cycloreversion of the 2-thioxothiazetidine 7 (CS2 elimination). The [4+2] addition of 4 occurs exclusively on the carbon-sulfur bond of isothiocyanates. Some differences are observed for additions of phenyl isocyanate to heterodienes 2 and 4. The regiochemical preferences in all cycloaddition and ring contraction reactions have been demonstrated.
引用
收藏
页码:623 / 634
页数:12
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