This paper reports the synthesis of the aryl(iodomethyl)phosphinic acid ethyl esters, Ar(ICH₂)P(O)OEt (Ar = Ph, Ar = mesityl), which, via dimethyamination, are converted to the corresponding aryl(dimethylaminomethyl)phosphinic acid ethyl esters, Ar(Me₂NCH₂)P(O)OEt (Ar = Ph, Ar = mesityl). Upon reaction with hydrogen chloride, compound Me₂NCH₂(Ph)P(O)OEt forms its hydrochloride salt as a crystalline material. Depending on the reaction conditions, treatment of Me₂NCH₂(Ph)P(O)OEt with SnCl₂ gave either [Me₂HNCH₂(Ph)P(O)OEt][SnCl₃] or the mixed‐valent dinuclear tin salt [{Me₂HNCH₂(Ph)P(O)O}₄SnCl₂][SnCl₃]₂, as its dichloromethane solvate. The reaction of Me₂NCH₂(Mes)P(O)OEt with SiMe₃I gives the diorgano bis(trimethylsiloxy)phosphinium iodide [Me₂NCH₂(Mes)P(OSiMe₃)₂]I, as its toluene solvate. In solution, it is involved in an equilibrium with Me₂NCH₂(Mes)P(O)OSiMe₃ and SiMe₃I. From the hydrolysis of [Me₂NCH₂(Mes)P(OSiMe₃)₂]I, the hydrogen iodide derivative [Me₂HNCH₂(Mes)P(O)OH]I was obtained as three different solvates. [Me₂NCH₂(Mes)P(OSiMe₃)₂]I reacted with SnF₂ to give a product mixture from which the mixed‐valent tin compound [{Sn^II₂Me₂NCH₂(Mes)P(O)₂}₄Sn^IVF₂]I₂, was isolated. The compounds were characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single‐crystal X‐ray diffraction analysis.

中文翻译：

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芳基（二甲基氨基甲基）次膦酸酯：卤素氢酸，卤化锡和三甲基卤代硅烷的合成，结构和反应

本文报道了芳基（碘甲基）次膦酸酯乙酯Ar（ICH ₂）P（O）OEt（Ar = Ph，Ar = mesityl）的合成，该化合物通过二甲基化作用转化为相应的芳基（二甲基氨基甲基）次膦酸酯乙酯，Ar（Me ₂ NCH ₂）P（O）OEt（Ar = Ph，Ar =均三甲苯基）。与氯化氢反应后，化合物Me ₂ NCH ₂（Ph）P（O）OEt形成盐酸盐，为结晶物质。根据反应条件，用SnCl ₂处理Me ₂ NCH ₂（Ph）P（O）OEt可以得到[Me ₂ HNCH ₂（Ph）P（O）OEt] [SnCl ₃]或混合价的双核锡盐[{Me ₂ HNCH ₂（Ph）P（O）O} ₄ SnCl ₂ ] [SnCl ₃ ] ₂为其二氯甲烷溶剂化物。Me ₂ NCH ₂（Mes）P（O）OEt与SiMe ₃ I的反应生成二有机双（三甲基甲硅烷氧基）碘化碘[Me ₂ NCH ₂（Mes）P（OSiMe ₃）₂ ] I，作为其甲苯溶剂化物。在溶液中，它与Me ₂ NCH ₂（Mes）P（O）OSiMe ₃和SiMe ₃ I处于平衡状态。[Me ₂的水解获得NCH ₂（Mes）P（OSiMe ₃）₂ ] I，作为三种不同的溶剂化物，得到碘化氢衍生物[Me ₂ HNCH ₂（Mes）P（O）OH] I。[Me ₂ NCH ₂（Mes）P（OSiMe ₃）₂ ] I与SnF ₂反应，得到一种产物混合物，混合后的锡化合物[{Sn ^II ₂ Me ₂ NCH ₂（Mes）P（O）₂ } ₄ Sn ^IV F ₂ ] I ₂，已被隔离。通过NMR和IR光谱，电喷雾电离质谱和单晶X射线衍射分析对化合物进行了表征。