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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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摘要

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 pK(a)> 7-8 gave the desired products. For less basic amines, reductiveN-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 R2NCH2OH and [R2N(CH2OH)(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-膦酸，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/或用于合成其他氨基烷基磷酸酸的生物活性类似物。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）与仲胺和湿法甲醛的反应在几乎定量的产率和几乎没有副产品的氨基甲基-H-膦酸中。令人惊讶的是，反应结果取决于胺的碱度。具有PK（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）的氧化结合的再生 - 甲基化成为相关的副反应。原发性胺对非常明显的胺类反应，仅获得氨基 - 双（甲基-H-膦酸），仅用于非常碱性胺。醛较高的反应产率较低。得到独特的羧 - 膦酸 - 膦酸以及来自多胺的聚胺（H-膦酸）。在P-H键氧化中示出了氨基烷基-H-膦酸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，例如常见的聚氮杂族缩醛，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。在反应机制中，达到羟基烷基物质R 2 NCH 2 OH和[R2N（CH 2 OH）（2）]（+），可能稳定为乙酸酯酯，作为反应性中间体。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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  • 来源
    《RSC Advances》 |2020年第36期|共21页
  • 作者

    Urbanovsky Peter; Kotek Jan; Cisarova Ivana; Hermann Petr;

  • 作者单位

    Charles Univ Prague Fac Sci Dept Inorgan Chem Univ Karlava Hlavova 8-2030 Prague 12843 2 Czech Republic;

    Charles Univ Prague Fac Sci Dept Inorgan Chem Univ Karlava Hlavova 8-2030 Prague 12843 2 Czech Republic;

    Charles Univ Prague Fac Sci Dept Inorgan Chem Univ Karlava Hlavova 8-2030 Prague 12843 2 Czech Republic;

    Charles Univ Prague Fac Sci Dept Inorgan Chem Univ Karlava Hlavova 8-2030 Prague 12843 2 Czech Republic;

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