2，6-二甲基吗啉及其衍生物的合成和工艺研究
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摘要
2,6-二甲基吗啉是一种重要的农药和医药中间体,本文以浓硫酸为催化剂和溶剂,由二异丙醇胺在低温和高温两种不同的环境下环化脱水制备2,6-二甲基吗啉,并研究其最优条件,获得最好的产率88.59%。同时,利用精馏柱来研究其顺反-2,6-二甲基吗啉以及水的分离工艺,获得纯度99%以上的顺式-2,6-二甲基吗啉和反式-2,6-二甲基吗啉。接着,我们对反式-2,6-二甲基吗啉的异构化进行了研究,采用不同的复合金属为催化剂,将反式-2,6-二甲基吗啉在最优化的条件下转化为顺式-2,6-二甲基吗啉,其最优的产率达到50%,选择性达到了90%。另外,本文也完成了2,6-二甲基吗啉的下游产品顺式-2,6-二甲基-4-异十三烷基吗啉的合成路线。采用顺式-2,6-二甲基吗啉,在碳酸钠为碱性催化剂的条件下,和溴代异十三烷在110℃脱溴化氢获得,产率可以达到79.32%。
2, 6-dimethyl-morpholine is very important mesial Substance of curative and safeguard reagent of agriculture. In this paper ,with diisopropanolamine containing from 0 to 20 of water for the raw material, 2, 6-dimethyl-morpholine could be synthesized with the overall yield of 88.59%. The reaction conditions were reaction at different temperatures (high temperature and low temperature), concentrated sulfuric acid as the catalyst and solvent. At the same time, we researched the arts and crafts of separate cis-2, 6-dimethyl- morpholine, tran-2, 6-dimethyl-morpholine and water used by rectification, obtaining cis-2,6-dimethyl-morpholine and tran-2, 6-dimethyl-morpholine with 99% pureness. continuity, we also researched the isomerization of cis-2, 6-dimethyl- morpholine, cis-2, 6-dimethyl- morpholine was manufactured by catalytic isomerization of tran-2, 6-dimethyl-morpholine at the optimum condition with different metal complex as catalyst. The optimum yield could reach 50% and best selectivity also could reach 90%.
In addition, we were also seeing about the preparation route of the downriver product of 2, 6-dimethyl-morpholine.With 2, 6-dimethyl-morpholine and 1-bromo- isotridecane as raw material ,2, 6-dimethyl-4-isotridecyl-morpholine was produced at 110℃temperature,Na_2CO_3 as the catalyst. The yield could reach 79.32%.
2, 6-dimethyl-morpholine is very important mesial Substance of curative and safeguard reagent of agriculture. In this paper ,with diisopropanolamine containing from 0 to 20 of water for the raw material, 2, 6-dimethyl-morpholine could be synthesized with the overall yield of 88.59%. The reaction conditions were reaction at different temperatures (high temperature and low temperature), concentrated sulfuric acid as the catalyst and solvent. At the same time, we researched the arts and crafts of separate cis-2, 6-dimethyl- morpholine, tran-2, 6-dimethyl-morpholine and water used by rectification, obtaining cis-2,6-dimethyl-morpholine and tran-2, 6-dimethyl-morpholine with 99% pureness. continuity, we also researched the isomerization of cis-2, 6-dimethyl- morpholine, cis-2, 6-dimethyl- morpholine was manufactured by catalytic isomerization of tran-2, 6-dimethyl-morpholine at the optimum condition with different metal complex as catalyst. The optimum yield could reach 50% and best selectivity also could reach 90%.
In addition, we were also seeing about the preparation route of the downriver product of 2, 6-dimethyl-morpholine.With 2, 6-dimethyl-morpholine and 1-bromo- isotridecane as raw material ,2, 6-dimethyl-4-isotridecyl-morpholine was produced at 110℃temperature,Na_2CO_3 as the catalyst. The yield could reach 79.32%.
引文
[1]赵丽梅.吗啉的生产应用及市场分析.化工中间体,2005,(10):11-14
[2]韩秀山.吗啉的应用及生产科研概况.四川化工与腐蚀控制,2002,5(5):33-37
[3]王勋章,田振生.吗啉国内外现状及发展前景.化工科技,2005,13(5):63-67
[4]吕耀宏.N-异十三烷-2,6-二甲基吗啉的制备方法[P].CN:1923822,2006
[5]冯志祥.抗真菌药阿莫罗芬的合成.中国药物化学杂志,2000,10(1):64-65
[6]程能林.溶剂手册.化学工业出版社,1994:427-430
[7]王箴.化工词典.化学工业出版社,1992:1
[8]杨华.吗啉产需现状与开发前景.精细化工原料及中间体,2006,6:21-23
[9]Summers.Method of producing cis-2,6-dimethylmorpholine[P].US:3083202,1963
[10]Goetz.Preparation of cis-2,6-dimethylmorpholine[P].US:4212972,1980
[11]Goetz.Preparation of cis-2,6-dimethylmorpholine[P].US:4504363,1985
[12]Wolfgang H.E..Dehydrating 2,6-Dimethylmorpholine[P].US:4571284,1986
[13]Borsdorff H.W..Method of manufacturing cis-2,6-dimethylmorpholine[P].DE:3708931,1987
[14]Goetz.Preparation of cis-2,6-dimethylmorpholine[P].US:4298733,1981
[15]Pinkos R..Preparation of 2,6-dimethylmorpholine from N-(2-hydroxypropyl)-2,6- di methylmorpholine[P].US:5436335,1995
[16]高滋.沸石催化与分离技术.中国石化出版社,1999:462-497
[17]李肇凯.酸催化二甘醇脱水环化反应研究.金山油化纤,2006,1(25):8-12
[18]李肇凯.无机酸催化二甘醇脱水环化反应的催化作用.金山油化纤,2005,1(24):13-17
[19]马心如.恒沸精馏法生产无水酒精.酿酒科技,2002,2:57-58
[20]郭和刚.间歇恒沸精馏分离异丙醇水溶液的过程研究.天然气化工,2005,2(30):6-10
[21]王昇.水、丙二醇和丙二醇单甲醚混合物分离工艺.石油化工,2002,12(31):973-976
[22]张贤明.油水分离脱水新工艺及其应用实践.金属矿山,2001,7(301)
[23]胡兴兰,周荣琪.萃取精馏法分离醋酸-水的研究.环境污染治理技术与设备,2006,7(11):81-83
[24]白鹏.乙醇-水分批萃取精馏中溶剂的回收过程.江苏大学学报,2005,3(26):270-273
[25]白鹏.乙醇-水分批萃取精馏中溶剂流率的选择及溶剂的回收的研究.江苏大学学报,2005,2(23):256-260
[26]伍钦.传质与分离工程.华南理工大学出版社,2005
[27]张健远,康保安.Pd/C催化剂的表征及其制备条件对脂肪腈加氢催化的影响.皮革化 工,2006,2(23):10-15
[28]祝远较.以Pd/C为催化剂的松香加氢反应机理.化学研究与应用.2007,2(19):210-215
[29]王桂香,董国君.负载型Pd催化剂.化学工程师,2001,6(87):6-8
[30]李海涛,龚健.HZSM-5沸石在邻氯甲苯异构化反应中的择形催化作用.催化学报,2000,1(21):11-13
[31]夏道宏,罗立文.HZSM-5分子筛上异丁硫醇催化转化反应.石油学报,2004,5(20):66-70
[32]刘雪暖,李玉秋.Pd/HZSM-5催化剂异构化反应特性的研究.石油化工高等学校学报,2000,3(13):9-12
[33]王坤院,王祥生.改性纳米HZSM-5上对、邻二甲苯异构化反应性能的研究.石油学报,2007,6(23):13-17
[34]曹祖宾,徐贤伦.Pt/HZSM-5催化剂的制备因素对FCC汽油加氢异构化反应影响.石油化工高等学校学报,2003,2(16):45-50
[35]曹祖宾,徐贤伦.Pt/HZSM-5催化剂的制备因素对FCC汽油加氢异构化反应机理及动力学研究.分子催化,2003,2(17):111-117
[36]闫明珍.HZSM-5分子筛上异丁硫醇催化转化反应.石油学报.2004,5(20):64-70
[37]孟凡旭.Pd/HZSM-5涂层催化剂及正十二烷裂解.化学工业与工程.2007,5(24):385-388
[38]不同制备方法对醛胺缩合催化剂Pd/HZSM-5性能的影响.石油技术与应用.2003,4(21):246-248
[39]吴国旭,毕富春.烯唑醇的顺反立体异构体分析方法研究.农学环境科学学报2007,26(增刊):306-308
[40]郑建东.均匀设计法在制备吗啉合成催化剂中的应用.工业催化.2006,5(14):39-41
[2]韩秀山.吗啉的应用及生产科研概况.四川化工与腐蚀控制,2002,5(5):33-37
[3]王勋章,田振生.吗啉国内外现状及发展前景.化工科技,2005,13(5):63-67
[4]吕耀宏.N-异十三烷-2,6-二甲基吗啉的制备方法[P].CN:1923822,2006
[5]冯志祥.抗真菌药阿莫罗芬的合成.中国药物化学杂志,2000,10(1):64-65
[6]程能林.溶剂手册.化学工业出版社,1994:427-430
[7]王箴.化工词典.化学工业出版社,1992:1
[8]杨华.吗啉产需现状与开发前景.精细化工原料及中间体,2006,6:21-23
[9]Summers.Method of producing cis-2,6-dimethylmorpholine[P].US:3083202,1963
[10]Goetz.Preparation of cis-2,6-dimethylmorpholine[P].US:4212972,1980
[11]Goetz.Preparation of cis-2,6-dimethylmorpholine[P].US:4504363,1985
[12]Wolfgang H.E..Dehydrating 2,6-Dimethylmorpholine[P].US:4571284,1986
[13]Borsdorff H.W..Method of manufacturing cis-2,6-dimethylmorpholine[P].DE:3708931,1987
[14]Goetz.Preparation of cis-2,6-dimethylmorpholine[P].US:4298733,1981
[15]Pinkos R..Preparation of 2,6-dimethylmorpholine from N-(2-hydroxypropyl)-2,6- di methylmorpholine[P].US:5436335,1995
[16]高滋.沸石催化与分离技术.中国石化出版社,1999:462-497
[17]李肇凯.酸催化二甘醇脱水环化反应研究.金山油化纤,2006,1(25):8-12
[18]李肇凯.无机酸催化二甘醇脱水环化反应的催化作用.金山油化纤,2005,1(24):13-17
[19]马心如.恒沸精馏法生产无水酒精.酿酒科技,2002,2:57-58
[20]郭和刚.间歇恒沸精馏分离异丙醇水溶液的过程研究.天然气化工,2005,2(30):6-10
[21]王昇.水、丙二醇和丙二醇单甲醚混合物分离工艺.石油化工,2002,12(31):973-976
[22]张贤明.油水分离脱水新工艺及其应用实践.金属矿山,2001,7(301)
[23]胡兴兰,周荣琪.萃取精馏法分离醋酸-水的研究.环境污染治理技术与设备,2006,7(11):81-83
[24]白鹏.乙醇-水分批萃取精馏中溶剂的回收过程.江苏大学学报,2005,3(26):270-273
[25]白鹏.乙醇-水分批萃取精馏中溶剂流率的选择及溶剂的回收的研究.江苏大学学报,2005,2(23):256-260
[26]伍钦.传质与分离工程.华南理工大学出版社,2005
[27]张健远,康保安.Pd/C催化剂的表征及其制备条件对脂肪腈加氢催化的影响.皮革化 工,2006,2(23):10-15
[28]祝远较.以Pd/C为催化剂的松香加氢反应机理.化学研究与应用.2007,2(19):210-215
[29]王桂香,董国君.负载型Pd催化剂.化学工程师,2001,6(87):6-8
[30]李海涛,龚健.HZSM-5沸石在邻氯甲苯异构化反应中的择形催化作用.催化学报,2000,1(21):11-13
[31]夏道宏,罗立文.HZSM-5分子筛上异丁硫醇催化转化反应.石油学报,2004,5(20):66-70
[32]刘雪暖,李玉秋.Pd/HZSM-5催化剂异构化反应特性的研究.石油化工高等学校学报,2000,3(13):9-12
[33]王坤院,王祥生.改性纳米HZSM-5上对、邻二甲苯异构化反应性能的研究.石油学报,2007,6(23):13-17
[34]曹祖宾,徐贤伦.Pt/HZSM-5催化剂的制备因素对FCC汽油加氢异构化反应影响.石油化工高等学校学报,2003,2(16):45-50
[35]曹祖宾,徐贤伦.Pt/HZSM-5催化剂的制备因素对FCC汽油加氢异构化反应机理及动力学研究.分子催化,2003,2(17):111-117
[36]闫明珍.HZSM-5分子筛上异丁硫醇催化转化反应.石油学报.2004,5(20):64-70
[37]孟凡旭.Pd/HZSM-5涂层催化剂及正十二烷裂解.化学工业与工程.2007,5(24):385-388
[38]不同制备方法对醛胺缩合催化剂Pd/HZSM-5性能的影响.石油技术与应用.2003,4(21):246-248
[39]吴国旭,毕富春.烯唑醇的顺反立体异构体分析方法研究.农学环境科学学报2007,26(增刊):306-308
[40]郑建东.均匀设计法在制备吗啉合成催化剂中的应用.工业催化.2006,5(14):39-41
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