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白磷直接合成单膦化合物
作者:小柯机器人 发布时间:2021/4/7 13:21:13

德国雷根斯堡大学Robert Wolf团队报道了白磷直接合成单膦化合物。 相关研究成果发表在2021年4月5日出版的《自然—化学》。

单磷化合物由于在医药、光引发剂和催化配体等方面的重要应用而具有重要的工业应用价值。白磷(P4)是制备所有此类化学品的关键起始材料。然而,目前的生产依赖于间接的、低效的、多步骤的程序。

该文中,研究人员报告了一个简单、有效的'一锅'合成法,直接从P4合成广泛的有机和无机单磷物种。用三正丁基锡氢化物还原P4,然后用各种亲电试剂处理,得到对化学工业至关重要的化合物,并且只需要温和的条件和廉价易处理的试剂。

最关键的是,研究人员还展示了三丁基锡试剂的简易高效回收和最终催化使用,从而避免了大量含锡废物的形成。可获得的工业相关产品包括熏蒸剂PH3、还原剂次磷酸和阻燃剂前体四(羟甲基)氯化磷。

附:英文原文

Title: Synthesis of monophosphines directly from white phosphorus

Author: Daniel J. Scott, Jose Cammarata, Maximilian Schimpf, Robert Wolf

Issue&Volume: 2021-04-05

Abstract: Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications such as pharmaceuticals, photoinitiators and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends on indirect and inefficient, multi-step procedures. Here, we report a simple, effective ‘one-pot’ synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-n-butyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and it requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately catalytic use of the tributyltin reagent, thereby avoiding the formation of substantial Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride.

DOI: 10.1038/s41557-021-00657-7

Source: https://www.nature.com/articles/s41557-021-00657-7

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex