一种草铵膦合成新工艺

A New Synthetic Process of Glufosinate-ammonium

[目的]草铵膦合成新工艺的研究。[方法]以低廉的γ-丁内酯为原料,与溴素作用,选择性地发生α位单溴取代生成α-溴-γ-丁内酯,然后与氨水进行氨基化反应,加盐酸回流得到α-氨基-γ-丁内酯盐酸盐,氨基保护得到(2-氧代四氢呋喃-3-基)氨基甲酸乙酯,该中间体经氯化开环得到4-氯-2-乙氧羰基氨基丁酸乙酯,然后与甲基亚磷酸二乙酯进行Arbuzov反应,经酸化水解、氨化得到产物草铵膦。[结果]反应总收率为21%。[结论]本路线反应条件比较温和,污染较少,产率较高,降低了成本,适合工业化生产。

[Aims] A new synthetic route of glufosinate was studied.[Methods ] With low-cost γ-butyrolactone as starting material, it selectively reacted with bromine to generate α-bromo-γ-butyrolactone via α-monobromination, then aminated with ammonia water, and refluxed with hydrochloric acid to obtain α-amino-γ-butyrolactone hydrochloride, carried on amino-protection to obtain (2-oxo-tetrahydro-furan-3-yl)-carbamic acid ethyl ester, then it was through ring opening and chlorination to obtain 4-chloro-2-ethoxycarbonylamino-butyric acid ethyl ester, then it reacted with methyldiethoxyphosphine via Arbuzov reaction, acidified hydrolysis, and aminated to obtain the product glufosinate.[Re s ults ] The total reaction yield was 21%.[Conclusions ] This process has the advantages of warm reacting conditions, less waste, high yield and low cost. It is valuable to be used in industrial scale manufacture.