N-正丁基硫代磷酰三胺的绿色合成

Research on Green Synthesis of N-( n-Butyl) thiophosphoric Triamide

采用改进的"一锅法"合成了N-正丁基硫代磷酰三胺(NBPT),以氨气替代传统液相试剂作为缚酸剂及后续胺化反应的原料,考察了反应温度、原料摩尔比、氨气流速、通氨间歇时间和胺化反应温度对产品收率的影响。优化的实验条件为:反应温度为0℃,正丁胺(0.42 mol)与三氯硫磷(0.35 mol)的摩尔比为1.2∶1,氨气流速为15 m L/min,通氨间歇时间为30 min,胺化反应温度为10℃。在该条件下,NBPT收率达75.6%,粗产物纯度为97%。采用红外光谱(IR)、元素分析、核磁分析(NMR)和液相色谱-质谱联用仪(LC-MS)对样品进行了表征。该合成过程具有操作步骤简单,生产成本低,副产物只有氯化铵等特点,是一条绿色合成路线。

N-（ n-Butyl） thiophosphoric triamide（ NBPT） was synthesized successfully by modified ＂onepot＂ method. During the experiments,the ammonia was used as acid-binding agent to replace traditional liquid reagent and the raw materials of subsequent amination reaction. The effect of the reaction temperature,the mole ratio of substrates,the flow rate of ammonia,the intermittence time of flowing ammonia and the temperature of amination reaction on yield of the product were investigated.The optimized experimental parameters were as follows： the reaction temperature was 0 ℃,the mole ratio of n-butylamine（ 0. 42 mol） and thiophosphoryl chloride（ 0. 35 mol） was 1. 2∶1,ammonia flow rate was 15 m L / min,the intermittence time of flowing ammonia was 30 min and the temperature of amination reaction was 10 ℃. Under the optimized conditions,the yield of NBPT was 75. 6% and the purity was 97%. The sample with the highest yield was characterized by infrared spectroscopy（ IR）,elemental analysis,nuclear magnetic resonance spectrum（ NMR） and liquid chromatograph-mass spectrometer（ LC-MS）. The synthesis process,an innovative green one,had advantages of simple operation steps and low production cost. At the same time,the only by-product was ammonium chloride.