摘要
设计并合成了一种草铵膦的新型中间体2-乙酰氨基-4-[羟基(甲基)膦酰基]丁-2-烯酸。以乙酰氨基丙二酸二乙酯为初始原料,经水解,缩合反应得到终产物。该路线的反应条件如下:水解反应时,Na OH和原料摩尔比为1.02∶1,反应温度25℃~30℃,最佳反应时间16 h,中间物单乙酯的收率85.3%;缩合反应时,最佳投料摩尔比为n(单乙酯)∶n(膦醛)∶n(吡啶)∶n(乙酸酐)=1.1∶1∶10∶(3~4)时,缩合产物收率74%。最后对产物2-乙酰氨基-4-[羟基(甲基)膦酰基]丁-2-烯酸经1H NMR,13C NMR,31P NMR进行了表征。通过优化反应条件,总收率达到63.1%,该路线工艺简单,条件温和,适合工业生产。
The 2-acetamido-4-[hydroxy（methyl）phosphonyl]but-2-enoic acid,an intermediate for producingglufosinate-ammonium,was synthesized with diethyl acetamidomalonate as a start material through hydrolysisand condensation reactions. The yield of monoethyl ester was 85.3% by hydrolysis with 1.02∶1 mole ratio ofsodium hydroxide to diethylacetamidomalonate at 25 ℃-30 ℃ for 16 h. The yield of main products aftercondensation reached 74% with 1.1/1/10/（3-4）mole ratio of monoethyl ester/phosphonic aldehyde/pyridine/anhydride. Finally,the structures of the product,2-acetamido-4-[hydroxy（methyl）phosphonyl]but-2-enoicacid was characterized by1 H,13 C and31 P nuclear magnetic resonance spectroscopy. Its total yield ofintermediate is 63.1% under the optimum reaction conditions. This synthetic route is suitable in industryproduction with simple operation and mild conditions.
出处
《武汉工程大学学报》
CAS
2018年第1期17-22,共6页
Journal of Wuhan Institute of Technology
基金
湖北省自然科学基金(2012FFB04704)
