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首页> 外文期刊>RSC Advances >Selective and clean synthesis of aminoalkyl-H-phosphinic acids from hypophosphorous acid by phospha-Mannich reaction
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Selective and clean synthesis of aminoalkyl-H-phosphinic acids from hypophosphorous acid by phospha-Mannich reaction

机译：通过磷酸盐反应从次磷酸中选择和清洁氨基烷基-H膦酸的合成

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Aminoalkyl- H -phosphinic acids, also called aminoalkylphosphonous acids, are investigated as biologically active analogues of carboxylic amino acids and/or as valuable intermediates for synthesis of other aminoalkylphosphorus acids. Their synthesis has been mostly accomplished by phospha-Mannich reaction of a P–H precursor, an aldehyde and an amine. The reaction is rarely clean and high-yielding. Here, reaction of H _(3) PO _(2) with secondary amines and formaldehyde in wet AcOH led to aminomethyl- H -phosphinic acids in nearly quantitative yields and with almost no by-products. Surprisingly, the reaction outcome depended on the basicity of the amines. Amines with p K _(a) > 7–8 gave the desired products. For less basic amines, reductive N -methylation coupled with oxidation of H _(3) PO _(2) to H _(3) PO _(3) became a relevant side reaction. Primary amines reacted less clearly and amino-bis(methyl- H -phosphinic acids) were obtained only for very basic amines. Reaction yields with higher aldehydes were lower. Unique carboxylic–phosphinic–phosphonic acids as well as poly( H -phosphinic acids) derived from polyamines were obtained. Synthetic usefulness of the aminoalkyl- H -phosphinic was illustrated in P–H bond oxidation and its addition to double bonds, and in selective amine deprotection. Compounds with an ethylene-diamine fragment, e.g. most common polyazamacrocycles, are not suitable substrates. The X-ray solid-state structures of seventeen aminoalkyl-phosphinic acids were determined. In the reaction mechanism, N -hydroxyalkyl species R _(2) NCH _(2) OH and [R _(2) N(CH _(2) OH) _(2) ] ~(+) , probably stabilized as acetate esters, are suggested as the reactive intermediates. This mechanism is an alternative one to the known phospha-Mannich reaction mechanisms. The conditions can be utilized in syntheses of various aminoalkylphosphorus compounds.
机译：氨基烷基 - H-磷酸酸，也称为氨基烷基膦酸，作为羧基氨基酸的生物活性类似物和/或作为合成其它氨基烷基磷酸酸的物质的中间体。它们的合成主要是通过P-H前体，醛和胺的磷酸盐反应来实现的。反应很少是清洁和高产的。这里，H→（3）PO _（2）的反应在湿AcOH中与仲胺和甲醛导致氨基甲基-H-膦酸，几乎定量的产率，几乎没有副产物。令人惊讶的是，反应结果取决于胺的碱度。具有Pκ_（a）> 7-8的胺给出了所需的产品。对于较少的碱性胺，与H _（3）PO _（2）至H _（3）PO _（3）的氧化结合的还原N-甲基化成为相关的副反应。伯胺对非常碱性胺仅获得氨基 - 双（甲基 - H-磷酸酸）而反应。醛较高的反应产率较低。获得独特的羧基 - 膦酸以及衍生自多胺的聚（H-膦酸）。在P-H键氧化中示出了氨基烷基-H-膦的合成有用性及其与双键的添加剂，以及选择性胺脱保护。具有乙烯 - 二胺片段的化合物，例如乙烯 - 二胺片段。最常见的聚氮杂化族，不是合适的基材。测定了十七氨基烷基膦酸的X射线固态结构。在反应机理中，N-羟基烷基物质R _（2）NCH _（2）OH和[R _（2）N（CH _（2）OH）_（2）]〜（+），可能稳定为乙酸盐酯，被认为是反应性中间体。该机制是已知的磷群反应机制的替代方案。条件可用于各种氨基烷基磷酸化合物的合成。

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