甲基二氯化磷的合成

Synthesis of Methylphosphorus Dichloride

[方法]甲基二氯化磷是合成草铵膦的关键中间体,国内尚未工业化生产,文献报道的方法中存在反应压力高、产品纯度低、工艺经济性差等缺点。以1,1,2,2-四氯乙烷为溶剂,氯甲烷、三氯化铝和三氯化磷为原料,在80℃条件下反应6 h得到配合物CH3PCl4.AlCl3,然后在140℃条件下用铝还原,一边反应一边蒸馏得到产品甲基二氯化磷。[结果]分别试验了原料配比、反应时间、温度等因素对收率和纯度的影响,实验结果得出目标化合物纯度98.0%(GC),总收率76.2%。[结论]该工艺简单经济,反应条件温和,适合工业化生产。

[Methods] Methylphosphorus dichloride was a key intermediate for preparing glufosinate,which has not been available for industrial production in China.Various processes are known for the manufacture of methylphosphorus dichloride.However,they all have one or more of the following disadvantages： 1）the reaction has to be carried out at high atmospheric pressure,2）the product has a poor purity,3）the process lack economical operation.Herein,an improved process was provided.A mixture of methy chloride,aluminum cholride and phosphorus trichloride was stirred in 1,1,2,2-tetrachloroethane at 80 ℃ for 6 h to give a complex of CH3PCl4·AlCl3,which was reduced with Al at 140 ℃ and distilled to give methylphosphorus dichloride.[results] The acts of raw materials ratio,reaction time,and other factors on the yield and purity were tested.the results showed that the yield was 76.2% and purity was 98.0%（GC）.[Conclusions] Methy chloride,aluminum chloride and phosphorus trichloride were used as raw materials to prepare methyphosphorus dichloride by a simple and economical operation.The reaction condition is gental,and suit for industrial production.