三苯基膦和六氯乙烷肽偶联试剂的中间体研究

Studies on Some Itermediates of the Peptide Coupling Reagents Hexachloroethane and Triphenylphosphine

利用核磁共振磷谱(31P NMR),电喷雾质谱(ESI-MS)研究三苯基膦与六氯乙烷反应的溶剂效应,其中间体在二氧六环中磷谱为-39×10-6,质谱鉴定为二氧六环参与配位的五配位磷化合物,乙二醇二甲醚中为二氯三苯基膦的共价键化合物。Appel试剂与羧基活化产物在乙二醇二甲醚和二氧六环中也同为五配位的共价键中间体,ESI-MS也确证了其分子式结构。并对这些中间体的合成进行了磷谱跟踪。

The intermediates of the Appel coupling reagents were studied in acetonitrile,methylene dichloride,dimethoxyethane and dioxane by 31P NMR spectrum and ESI-MS.In dioxane a new high coordinated phosphorous compound with 31P NMR shift at-39 ×10-6 was observed.The ESI-MS showed that it could be a penta-coordinated phosphorous compound containing a dioxane.In dimethoxyethane the intermediate is dichlorodiphenylphosporane.The carboxyl activated intermediates were also studied in three solvents,31P NMR and ESI-MS confirm that they are penta-coordinated phosphorous compounds.