Experimental Teaching Center of Environment and Cleaner Production in Chemical Industry, Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology , No. 693, Xiongchu Street, Hongshan District, Wuhan 430073, China.
J Agric Food Chem. 2012 Jun 27;60(25):6279-85. doi: 10.1021/jf301025p. Epub 2012 Jun 15.
On the basis of glycine-dimethyl phosphite synthesis of glyphosate, a new synthesis approach of glyphosate, without using triethylamine and the establishment of triethylamine recovery equipment, was designed in the laboratory. The environmental pollutants were reduced. The influences of reactant amount (mol), reaction temperature (°C), and reaction time (min) on the glyphosate yield and purity were investigated. The results showed that the glyphosate yield and purity could be 80.12 and 86.31 wt %, respectively, under the optimum scheme for glyphosate yield (glycine consumption, 0.1 mol; dimethyl phosphite consumption, 0.12 mol; condensation reaction temperature, 50 °C; hydrochloric acid consumption in hydrolysis reaction, 0.35 mol; temperature of acidification with hydrochloric acid, 10 °C; adjusting hydrolysis product pH value, 1.0; time of dropping esterifying liquid into hydrochloric acid in hydrolysis reaction, 80 min; hydrolysis reaction temperature, 120 °C; and vacuum distillation time, 90 min), and the glyphosate yield and purity could be 77.92 and 94.94 wt %, respectively, under the optimum scheme for glyphosate purity (glycine consumption, 0.1 mol; dimethyl phosphite consumption, 0.1 mol; condensation reaction temperature, 50 °C; hydrochloric acid consumption in hydrolysis reaction, 0.35 mol; temperature of acidification with hydrochloric acid, 10 °C; adjusting hydrolysis product pH value, 1.5; time of dropping esterifying liquid into hydrochloric acid in hydrolysis reaction, 60 min; hydrolysis reaction temperature, 110 °C; and vacuum distillation time, 90 min). The product structures under the two schemes were confirmed by means of FTIR (Fourier transform infrared spectroscopy) and (1)H NMR ((1)H nuclear magnetic resonance spectroscopy).
在甘氨酸-亚磷酸二甲酯合成草甘膦的基础上，设计了一种新的草甘膦合成方法，无需使用三乙胺和建立三乙胺回收设备，从而减少了环境污染。考察了反应物用量（摩尔）、反应温度（℃）和反应时间（min）对草甘膦产率和纯度的影响。结果表明，在优化方案下（甘氨酸用量为 0.1 mol，亚磷酸二甲酯用量为 0.12 mol，缩合反应温度为 50℃，水解反应中盐酸用量为 0.35 mol，酸化盐酸温度为 10℃，调节水解产物 pH 值为 1.0，水解反应中滴加酯化液的时间为 80 min，水解反应温度为 120℃，真空蒸馏时间为 90 min），草甘膦的产率和纯度分别可达 80.12%和 86.31%wt，在优化方案下（甘氨酸用量为 0.1 mol，亚磷酸二甲酯用量为 0.1 mol，缩合反应温度为 50℃，水解反应中盐酸用量为 0.35 mol，酸化盐酸温度为 10℃，调节水解产物 pH 值为 1.5，水解反应中滴加酯化液的时间为 60 min，水解反应温度为 110℃，真空蒸馏时间为 90 min），草甘膦的产率和纯度分别可达 77.92%和 94.94%wt。两种方案下的产物结构均通过 FTIR（傅里叶变换红外光谱）和（1）H NMR（（1）H 核磁共振光谱）得到确认。
