Synthesis of mixed phosphorotrithioates from white phosphorus,Green Chemistry

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Synthesis of mixed phosphorotrithioates from white phosphorus
Green Chemistry ( IF 9.3 ) Pub Date : 2020-10-22 , DOI: 10.1039/d0gc02985h
Xinlei Huangfu _{1,

2,

3,

4,

5} , Yue Zhang _{1,

2,

3,

4,

5} , Peiyun Chen _{1,

2,

3,

4,

5} , Guozhang Lu _{1,

2,

3,

4,

5} , Yinwei Cao _{1,

2,

3,

4,

5} , Guo Tang _{1,

2,

3,

4,

5} , Yufen Zhao _{1,

2,

3,

4,

5}

Affiliation

The first general and high-yielding synthesis of mixed phosphorotrithioates (R¹S)₂P(O)SR² involving white phosphorus, disulfides, and alkyl halides is presented, which provides the shortest and environmentally benign method to synthesize these compounds of practical importance. Only one method for the formation of (R¹S)₂P(O)SR² from elemental phosphorus has been developed. Here, with the use of KOH as a base and DMSO–toluene as a solvent, various disulfides couple readily with white phosphorus to give O-potassium S,S-dialkylphosphorotrithioates (R¹S)₂P(S)OK in almost quantitative yields, which react with alkyl halides to form (R¹S)₂P(O)SR² in high yields. The reaction is characterized by the complete conversion of white phosphorus. Moreover, this method can be easily adapted to large-scale preparation. Our mechanistic data suggest that the attack of RSK on S,S,S-trialkyl phosphorotrithioates and subsequent C–S bond cleavage, the Michaelis–Arbuzov-like dealkylation, are the key steps in the formation of (R¹S)₂P(S)OK.

中文翻译：

由白磷合成混合的三硫代磷酸酯

提出了涉及白磷，二硫化物和烷基卤化物的混合三硫代磷酸酯（R ¹ S）₂ P（O）SR ²的第一个常规且高产的合成方法，该方法提供了最短且对环境无害的方法来合成具有实际重要性的化合物。仅开发了一种由元素磷形成（R ¹ S）₂ P（O）SR ^2的方法。在这里，以KOH为碱，以DMSO-甲苯为溶剂，各种二硫化物容易与白磷偶合，得到O-钾S，S-二烷基三硫代磷酸酯（R ¹ S）₂P（S）OK的定量收率很高，可与卤代烷反应生成高收率的（R ¹ S）₂ P（O）SR ²。该反应的特征在于白磷的完全转化。而且，该方法可以容易地适于大规模制备。我们的机制数据表明，RSK攻击S，S，S-三烷基三硫代磷酸酯以及随后的C–S键裂解（Michaelis–Arbuzov样脱烷基）是（R ¹ S）₂ P（好）

更新日期：2020-11-05

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