Abstract Tetrakis(hydroxymethyl)phosphonium (HOCH2)4P+ salts, particularly the chloride (THPC) and sulfate (THPS), are among the most accessible organophosphorus compounds that can be made quantitatively from PH3 and formaldehyde in aqueous media under ambient conditions. These phosphonium salts are air-stable, and are widely used as reactants in organic syntheses, as well as in textile or oil industries. Synthesis of tris(hydroxymethyl)phosphine (THP), an active component of the salts, is more complicated because direct synthesis from PH3 and CH2O requires either pressure and high temperature, at which THP rearranges into bis(hydroxymethyl)methylphosphine oxide, CH3P(O)(CH2OH)2, or a metal catalyst that is usually difficult or impossible to recover. Syntheses of THP based on neutralization of the salts are more convenient but require pH control and additional steps to separate THP from CH2O. This review summarizes literature data on syntheses and purification of the salts and THP, and side reactions such as thermal rearrangement and oxidation. Graphical Abstract

中文翻译：

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三（羟甲基）膦和四（羟甲基）鏻盐的合成和重排

摘要 四（羟甲基）鏻 (HOCH2)4P+ 盐，尤其是氯化物 (THPC) 和硫酸盐 (THPS)，是最容易获得的有机磷化合物之一，可在环境条件下在水性介质中由 PH3 和甲醛定量制备。这些鏻盐在空气中稳定，广泛用作有机合成以及纺织或石油工业中的反应物。三（羟甲基）膦（THP）是盐类的一种活性成分，其合成更为复杂，因为从 PH3 和 CH2O 直接合成需要压力和高温，在高温下，THP 重排成双（羟甲基）甲基氧化膦，CH3P(O) )(CH2OH)2，或通常难以或不可能回收的金属催化剂。基于盐中和的 THP 合成更方便，但需要控制 pH 值和额外的步骤以将 THP 与 CH2O 分离。本综述总结了有关盐类和 THP 的合成和纯化以及副反应（如热重排和氧化）的文献数据。图形概要