草铵膦的绿色合成工艺
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摘要
[目的]草铵膦合成的绿色工艺研究。[方法]以甲基亚磷酸二乙酯为原料,与丙烯醛反应生成1-二乙氧基-3-(乙氧基甲基膦酰基)丙烷,经稀酸水解得到3-(甲基羟基膦酰基)丙醛,再与碳酸氢铵及氢氰酸利用Bucherer-Bergs反应环合,经氧化钙水解,二氧化碳通入反应液去除钙离子得到草铵膦。[结果]水解反应的最佳条件:投料量摩尔比例n(甲基亚磷酸二乙酯)∶n(氧化钙)∶n(水)为1∶2∶35,反应温度140℃,反应时间10 h。[结论]草铵膦的总收率可达70%。该方法合成草铵膦的工艺后处理简单,反应生成的副产品碳酸钙可以焙烧处理后以氧化钙形式套用,同时生成的二氧化碳也可回收循环利用。该工艺避免了废固的产生,可实现草铵膦的绿色生产。
[Aims] This study aims to develop a green process for glufosinate. [Methods] 1-Diethoxy-3-(ethoxymethylphosphoryl)propane was obtained by reacting diethoxyl methylphosphine with acrolen, and followed by hydrolysis with dilute sulfuric acid to give 3-[hydroxy(methyl)phosphoryl]propionaldehyde. The Bucherer-Bergs reaction of the aldehyde with ammonium bicarbonate and hydrogen cyanide afforded a hydantoin derivative, ethyl 2-(2,5-dioxoimidazolidin-4-yl)ethyl(methyl)phosphinate, which was hydrolyzed by calcium hydroxide and then introduced carbon dioxide into reaction system for removing calcium cations to give glufosinate. [Results] The optimal molar ratio of hydrolysis reaction is 1∶2∶35(diethoxyl methylphosphine: calcium oxide: water). The optimum reaction temperature is 140 ℃ and the reaction time is 10 h. [Conclusions] The total yield of glufosinate is up to 70%. The process for glufosinate is simple, economic and green, as the by-product calcium carbonate can be process to recycle.The process avoids the generation of waste solids and realizes the green production of glufosinate.
[Aims] This study aims to develop a green process for glufosinate. [Methods] 1-Diethoxy-3-(ethoxymethylphosphoryl)propane was obtained by reacting diethoxyl methylphosphine with acrolen, and followed by hydrolysis with dilute sulfuric acid to give 3-[hydroxy(methyl)phosphoryl]propionaldehyde. The Bucherer-Bergs reaction of the aldehyde with ammonium bicarbonate and hydrogen cyanide afforded a hydantoin derivative, ethyl 2-(2,5-dioxoimidazolidin-4-yl)ethyl(methyl)phosphinate, which was hydrolyzed by calcium hydroxide and then introduced carbon dioxide into reaction system for removing calcium cations to give glufosinate. [Results] The optimal molar ratio of hydrolysis reaction is 1∶2∶35(diethoxyl methylphosphine: calcium oxide: water). The optimum reaction temperature is 140 ℃ and the reaction time is 10 h. [Conclusions] The total yield of glufosinate is up to 70%. The process for glufosinate is simple, economic and green, as the by-product calcium carbonate can be process to recycle.The process avoids the generation of waste solids and realizes the green production of glufosinate.
引文
[1]刘长令,韩亮,李正名.以天然产物为先导化台物开发的农药品种(3)---除草剂[J].农药,2004,43(1):1-4.
[2]苏少泉.生物除草剂的研究与开发[J].农药,2004,43(3):97-100.
[3]张一宾.近年来全球草铵膦的市场及发展趋势[J].农药,2016,55(5):314-316.
[4]俞传明,刘宣淦.草铵膦的合成[J].农药,2001,40(4):1,15.
[5]杜春华,余俐佳,任志超.草铵膦铵盐及其中间体的合成[J].农药,2012,51(5):331-333.
[6]南开大学元素有机化学研究所编译.国外农药进展[M].北京:化学工业出版社,1990:212.
[7]TAKAMASTU H.Process for Producing Phosphinylamino Acid Derivatives:US,4906764[P].1990-03-06.
[8]ZEISS H J.Process for the Preparation of L-Homoalanin-4-yl(methyl)Phosphinic Acid and Its Alkyl Esters:US,4777279[P].1988-10-11.
[9]WILLMS L H.Method for Producing Glufosiantes and Intermediate Products for the Same:US,6359162[P].2002-03-19.
[10]杜晓华,李以名,徐振元.一种草铵膦的制备方法:CN,102584893[P].2012-07-18.
[11]宋宏涛,楚士晋.草铵膦制备合成方法简述[J].现代农药,2006,5(3):1-3.
[12]杜辉,孙春楼,邢柳.草铵膦的合成新工艺[J].农药,2018,57(11):799-801.
[2]苏少泉.生物除草剂的研究与开发[J].农药,2004,43(3):97-100.
[3]张一宾.近年来全球草铵膦的市场及发展趋势[J].农药,2016,55(5):314-316.
[4]俞传明,刘宣淦.草铵膦的合成[J].农药,2001,40(4):1,15.
[5]杜春华,余俐佳,任志超.草铵膦铵盐及其中间体的合成[J].农药,2012,51(5):331-333.
[6]南开大学元素有机化学研究所编译.国外农药进展[M].北京:化学工业出版社,1990:212.
[7]TAKAMASTU H.Process for Producing Phosphinylamino Acid Derivatives:US,4906764[P].1990-03-06.
[8]ZEISS H J.Process for the Preparation of L-Homoalanin-4-yl(methyl)Phosphinic Acid and Its Alkyl Esters:US,4777279[P].1988-10-11.
[9]WILLMS L H.Method for Producing Glufosiantes and Intermediate Products for the Same:US,6359162[P].2002-03-19.
[10]杜晓华,李以名,徐振元.一种草铵膦的制备方法:CN,102584893[P].2012-07-18.
[11]宋宏涛,楚士晋.草铵膦制备合成方法简述[J].现代农药,2006,5(3):1-3.
[12]杜辉,孙春楼,邢柳.草铵膦的合成新工艺[J].农药,2018,57(11):799-801.
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