双烷基膦酸的合成和性质研究

Syntheses and Properties of Di-tertiary Alkylphosphinic Acids

用格氏试剂与三氯化磷反应，继而水解、氧化，合成了３个高位阻双烷基膦酸，发现制备高位阻格氏试剂用叔氯代烷比叔溴代烷效果好；同时还用格氏试剂与亚磷酸酯反应，然后用Ｔｏｄｄ方法制备了二正辛基膦酸，发现亚磷酸二正丁酯比亚磷酸二乙酯反应效果好。此外，还考察了其１Ｈ、１３Ｃ、３１ＰＮＭＲ和酸电离性质与其取代基结构效应的关系。

Di-t-butyl,di-t-pentyl,di-t-octyl phosphinic acids were synthesized by the reaction of Grignard reagents with phosphorus trichloride,followed by oxidation with 30 percent hydrogen peroxide.The preparation of Grignard reagent from tertalkylchlorides is easier than that from tertalkylbromides,The structural identification and stereochemical analysis were also studied by pKa values,MS and 1H,13C,31P NMR.