Abstract

Hydrolysis of quaternary arylphosphonium zwitterions bearing COO⁻ and those in situ generated from the corresponding salts bearing Ac or OH at the aryl ring by using excess t-BuOK and stoichiometric water affords tertiary arylphosphine oxides in moderate to excellent yield, in contrast to hydrolysis of these zwittertion or salts in aqueous NaOH that mainly provides phosphine oxides with the loss of the aryl group. Under the t-BuOK/water conditions, hydrolysis of carbonyl stabilized ylides Ph₃P = CHCOR (R = Ph, Me, and OEt), which partially exist as phosphonium enolates, prefers to produce Ph₂P(O)CH₂COR. Further reduction of Ph₂P(O)CH₂COMe by PhSiH₃ allows the preparation of Ph₂PCH₂COMe in 43% yield.

摘要

季芳基鏻两性离子轴承COO的水解^-和那些在从轴承AC或OH在芳基环的相应的盐原位产生通过使用过量吨-BuOK和化学计量的水，得到的叔芳基膦氧化物在中度至良好产率，相反，这些水解在NaOH水溶液中的两性分馏或盐类，主要是使氧化膦失去芳基。在t- BuOK /水条件下，部分以磷烯醇phospho形式存在的羰基稳定化的烷基化物Ph ₃ P = CHCOR（R = Ph，Me和OEt）的水解更倾向于生成Ph ₂ P（O）CH ₂ COR。Ph ₂ P（O）CH _2的进一步还原PhSiH ₃的COMe可以43％的收率制备Ph ₂ PCH ₂ COMe。