TERTIARY PHOSPHANE-TETRACHLOROMETHANE, A VERSATILE REAGENT FOR CHLORINATION, DEHYDRATION, AND P-N LINKAGE
TERTIARY PHOSPHANE-TETRACHLOROMETHANE, A VERSATILE REAGENT FOR CHLORINATION, DEHYDRATION, AND P-N LINKAGE
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DOI：
10.1002/anie.197508011
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发表时间：
1975-01-01
期刊：
影响因子：
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通讯作者：
APPEL, R
中科院分区：
文献类型：
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作者：
APPEL, R
在这篇综述中，首次报道了用四氯甲烷处理三苯基膦的过程;在这里，（三氯甲基）氯化鏻起着关键作用，它与进一步量的膦反应，通过二氯膦和（二氯亚甲基）膦的方式得到稳定的盐[氯（三苯基膦二基）甲基]三苯基氯化鏻，它只能作为中间体检测。作为氯化、脱水和P-N-连接试剂的双组分体系的制备应用归因于通过几种反应性物质对所讨论的底物的“磷酸化”。在这些应用中，与底物的反应与双组分体系与自身的反应竞争，因此反应的整个过程几乎在所有情况下都比以前假设的要复杂得多。尽管如此。通过使用该试剂可以获得非常好的结果，高产率和温和的反应条件是其特征。
In this review the processes occurring on the treatment of triphenylphosphane with tetrachloromethane are first reported; a key role is played here by (trichloromethyl)phosphonium chloride which reacts with a further amount of the phosphane to give the stable salt [chloro(triphenylphos‐phoranediyl)methyl]triphenylphosphonium chloride by way of dichlorophosphorane and (dichloromethylene)phosphorane that is detectable only as an intermediate. The preparative application of the two‐component system as a chlorinating, dehydrating, and P—N‐linking reagent is ascribable to “phosphorylation” of the substrate in question through several reactive species. In these applications the reactions with the substrate compete with reactions of the two‐component system with itself, so that the overall course of the reaction is in nearly all cases much more complex than was previously assumed. Nevertheless. very good results can be achieved by the use of this reagent, high yields and mild reaction conditions being characteristic.