3-甲氧基丙胺的合成研究
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摘要
3-甲氧基丙胺,别名：Y-甲氧基丙胺,在染料和水处理剂及缓蚀剂方面的应用广泛。根据文献分析,对3-甲氧基丙胺的两种合成路线进行综合对比,创新地提出了一种全新的合成工艺路线,即以甲醇与丙烯腈为原料,先制得3-甲氧基丙腈,然后通过连续法催化剂加氢来制得3-甲氧基丙胺。
本文主要以甲醇与丙烯腈为原料制备3-甲氧基丙腈,然后以3-甲氧基丙腈为原料,连续加氢制备3-甲氧基丙胺的工艺进行了研究。当反应温度40-45℃,用30%NaOH为催化剂,甲醇：丙烯腈(摩尔比)=1.1：1时,丙烯腈的转化率接近100%。将粗品3-甲氧基丙腈进行甲醇脱除,得到的甲醇套用做3-甲氧基丙腈,得到的纯3-甲氧基丙腈作为加氢原料。在加氢过程中,确定了合适的工艺条件：在加氢釜中加入纯的3-甲氧基丙胺和催化剂、抑制剂,通入氢气,控制反应温度90℃,反应压力2.5MPa,用计量泵将纯3-甲氧基丙腈打入加氢釜中。在此种条件下,3-甲氧基丙胺的收率≥99%。
3-Methoxypropan-l-amine (MOPA), also named y-methoxy propane-1-amine, is a widely used raw chemical material and fine chemical intermediate. In this dissertation, we compared two preparation processes of MOPA, and proposed a new chemical process to synthesize MOPA with great potential in industrialisation.
The process includes two steps:i)3-methoxy propionitrile is prepared with methanol and acrylonitrile as raw materials; ii) MOPA is prepared by continuous hydrogenation of3-methoxypropionitrile. In the first step, the optimized conversion of acrylonitrile is nearly100%under the reaction temperature range from40to45C, using30%NaOH as catalyst, and1.1:1molar ratio of methanol:acrylonitrile. After distilled excess methanol, pure3-Methoxy propionitrile is obtained. The recycled methanol is used for the next batch. In the second step, MOPA is obtained with catalytic hydrogenation, with a yield higher than99%, keeping the reaction temperature at90C, and pressure at2.5MPa.
本文主要以甲醇与丙烯腈为原料制备3-甲氧基丙腈,然后以3-甲氧基丙腈为原料,连续加氢制备3-甲氧基丙胺的工艺进行了研究。当反应温度40-45℃,用30%NaOH为催化剂,甲醇：丙烯腈(摩尔比)=1.1：1时,丙烯腈的转化率接近100%。将粗品3-甲氧基丙腈进行甲醇脱除,得到的甲醇套用做3-甲氧基丙腈,得到的纯3-甲氧基丙腈作为加氢原料。在加氢过程中,确定了合适的工艺条件：在加氢釜中加入纯的3-甲氧基丙胺和催化剂、抑制剂,通入氢气,控制反应温度90℃,反应压力2.5MPa,用计量泵将纯3-甲氧基丙腈打入加氢釜中。在此种条件下,3-甲氧基丙胺的收率≥99%。
3-Methoxypropan-l-amine (MOPA), also named y-methoxy propane-1-amine, is a widely used raw chemical material and fine chemical intermediate. In this dissertation, we compared two preparation processes of MOPA, and proposed a new chemical process to synthesize MOPA with great potential in industrialisation.
The process includes two steps:i)3-methoxy propionitrile is prepared with methanol and acrylonitrile as raw materials; ii) MOPA is prepared by continuous hydrogenation of3-methoxypropionitrile. In the first step, the optimized conversion of acrylonitrile is nearly100%under the reaction temperature range from40to45C, using30%NaOH as catalyst, and1.1:1molar ratio of methanol:acrylonitrile. After distilled excess methanol, pure3-Methoxy propionitrile is obtained. The recycled methanol is used for the next batch. In the second step, MOPA is obtained with catalytic hydrogenation, with a yield higher than99%, keeping the reaction temperature at90C, and pressure at2.5MPa.
引文
[1]Streitwiser A., Jr. et al., Introduction to organic chemistry, MacMillan, New York.,1981, 765.
[2]E.卡特梅尔等著,宁世光译,原子价与分子结构,人民教育出版社,北京,1981,164.
[3]Fieser L. F., et al., Advanced organic chemistry, Reinhold, New York, 1961,620
[4]A.E.奇奇巴宾著,叶秀林等译,有机化学基本原理,下册,高等教育出版社,北京,1965,398.
[5]Makosza M., Winiask J., Vicarious nucleophilic substitution of hydrogen. Acc. Chem. Res.,1987,20:282-288.
[6]Katrizky A. R., Laurenzo K. S., Alkylaminoonitrobenzenes by vicarious nucleophilic amnination with 4-(alkylamion)-1,2,4-uiazoles. J. Org. Chem.,1988, 53:3978-3982.
[7]Praefcke K., Kone B., DE 3612238[P], Chem. Abstr.,1988,108:159109
[8]Makosza M., Bialecki M., Amination of nitroarenes with sulfenamides via vicarious nucleophilic substitution of hydrogen. J. Org. Chem.,1992,57:4784-4785.
[9]Pagoria P. F., Mitchell A. R., Schmidt R. D.,1,1,1-Trimethylhydrazinium iodide:a novel, highly reactive reagent for aromatic amination via vicarious nucleophilic substitution of hydrogen. J. Org. Chem., 1996, 61: 2934-2935.
[10]Makosza M., Bialecki M., Nitroarylamines via the vicarious nucleophilic substitution of hydrogen: amination, alkylamination and arylamination of nitroarenes with sulfenamides. J. Org. Chem.,1998,633: 4878-4888.
[11]Schmidt R. D., Mitchell A. R., Pagoria P. F., New synthesis of TATB process development.29th International Annual Conference of ICT, Karlsruhe, Germany, 2000.
[12]Schmidt R. D., Mitchell A. R., Lee G. S., et al., New synthesis of TATB-scaleup and product charaterization. 31th International Annual Conference of ICT, Karlsruhe, Germany, 2000.
[13]Makosza M., Lemek T., Kwast A., et al. Elucidation of the vicarious nucleophilic substitution of hydrogen mechanism via studies of competition between substitution of hydrogen, deuterium, and fluorine. J. Org. Chem., 2002, 67: 394-400.
[14]Li J. S., Huang Y. G., Dong H. S., et al., Density fuctional theory study on polynitropyridines. Chinese J. Energ. Mater.,2003, 11:178-181.
[15]Li J. S., Huang Y. G, Dong H. S., Theoretical prediction of properties of polynitropyridines and their noxides. Chinese J. Energ. Mater., 2004,12:576-579.
[16]赵晓峰,刘祖亮,氨基硝基啶及其氮氧化合物的亲核取代胺化反应.应用化学2011,28(4)：376-380.
[17]Imao D., Fujihara S., Yamamoto T., et al. Efiective reductive amination of carbowl compounds with hydrogen catalyzed by iridium complex in organic solvent and in ionic liquid. Tetrahedron. 2005,61:6988-6992.
[18]罗书平,许丹倩,张帆等.离子液体中芳香醛选择性还原胺化反应研究.高等化学工程学报,2006,20：306-309.
[19]Reddy P., Kanjilal S., Sunitha S., et al. Reductive amination ofcarbonyl compounds using NaBH4 in a Bronsted acidicionic liquid. Tetrahedron Lerers.,2007, 48: 8807-8810.
[20]傅滨,李楠,梁晓梅等.还原胺化反应的新进展.有机化学,2007,27：1-7.
[21]Xu G., Ww J. R, Yang L. R., Zincborohydride-ionicliquid: stable andeficient systemforreductive reactionofaldehydeswithprimary amines to corresponding secondary amines. Chem. Res. Chinese universities.2008,24:120-122.
[22]Elizabeth R., Burkhardt R., Reductive aminationwith 5-ethy, 1-2-methylpyridineborane. Tetrahedron Lett.,2008,49:5152-5155.
[23]田兰红,张惠欣,王家喜,冯磊.功能性离子液体的合成及其在还原胺化中得应用.河北工业大学学报,2011,40：60-63.
[24]Finar, I. L., Organic Chemistry, Longman, London.1973,367.
[25]Glould E. S., Mechanism and structure in organic chemistry, Holt-dryden, New York. 1960, 291.
[26]Mocasland G. E., et al., J. Am. Chem. Soc.,1950,72:2190.
[27]Williams R., Jr. et al., Chem. Eng. News.,1955,33:3982.
[28]Leonard N. J., et al., J. Am. Chem. Soc.,1959,81:5631.
[29]王海燕,陈群,孙富安,郭一,何明阳.脂肪聚醚醇催化胺化反应的研究,化学世界,2010,9：549-551.
[30]吕璐,曹一林,马跃.化学与粘合.2003,6：300-303.
[31]刘立峰,姜志国,周亨近等.北京化工大学学报,2005,32：103-105.
[32]乔迁,长春工业大学学报,2002,23：80-82.
[33]张士福,诸勤忠,杨朝东等.CN：1635012A,[P],2005.
[34]法拉J M,哈尔肖姆B M.CN：101001902,[P],2007.
[35]郁维铭.聚氨酯工业,2002,17：1-5.
[36]Lark J. M., Renken T. L., US:4766245, [P],1988.
[37]郁维铭,张金龙,杨艳等.CN：1546550,[P],2004.
[38]陈立功,精细化工原料及中间体,2005,2：3-4.
[39]Gould, E. S., Mechanism and structure in organic chemistry, Holt-Dryden, New York, 1960,452.
[40]章思贵,精细有机化学品技术手册,科学出版社,1991,882.
[41]徐显庭,3-甲氧基丙胺的制备,上海化工,2001,13：17-19.
[42]Sabatier P., Senderens J.B., Comptes Rendus, 1905,140:482.
[43]Mignonac G, Comptes Rendus.,1920, 171:114.
[44]Winans C.F., Adkins H., J. Am. Chem. Soc., 1932,54:306.
[45]Juday R., Adkins H., J. Am. Chem. Soc., 1955,77:4559.
[46]Jiang H. J., Tzou M. S., Sachtler W. M. H., Catal. Lett.,1988, 1: 99.
[47]Feeley J., Sachtler W.M.H.,J. Catal.,1991,131:573.
[48]TrevinAo H., Sachtler W. M. H., Catal. Lett.,1994,27:251.
[49]Chatterje A., Shaikh R. A., Raj A., SingA. P. H, Catal. Lett.,1995,31:301.
[50]Hochard F, Jobic H., Massardier J., Renouprez A. J., J. Mol. Catal. A.1995,95:165.
[51]Barrault J., Pouilloux Y, Catal. Today.1997,37:137.
[52]Rode C. V., Arai M., Shirai M., Nishiyama Y., Appl. Catal.,1997,148:405.
[53]Cabello F. M., Tichit D., Coq B., Vaccari A., Dung N. T., J. Catal.,1997,167:142.
[54]Huang Y, Sachtler W. M. H., Applied Catalysis A, 1999, 182:365-378.
[2]E.卡特梅尔等著,宁世光译,原子价与分子结构,人民教育出版社,北京,1981,164.
[3]Fieser L. F., et al., Advanced organic chemistry, Reinhold, New York, 1961,620
[4]A.E.奇奇巴宾著,叶秀林等译,有机化学基本原理,下册,高等教育出版社,北京,1965,398.
[5]Makosza M., Winiask J., Vicarious nucleophilic substitution of hydrogen. Acc. Chem. Res.,1987,20:282-288.
[6]Katrizky A. R., Laurenzo K. S., Alkylaminoonitrobenzenes by vicarious nucleophilic amnination with 4-(alkylamion)-1,2,4-uiazoles. J. Org. Chem.,1988, 53:3978-3982.
[7]Praefcke K., Kone B., DE 3612238[P], Chem. Abstr.,1988,108:159109
[8]Makosza M., Bialecki M., Amination of nitroarenes with sulfenamides via vicarious nucleophilic substitution of hydrogen. J. Org. Chem.,1992,57:4784-4785.
[9]Pagoria P. F., Mitchell A. R., Schmidt R. D.,1,1,1-Trimethylhydrazinium iodide:a novel, highly reactive reagent for aromatic amination via vicarious nucleophilic substitution of hydrogen. J. Org. Chem., 1996, 61: 2934-2935.
[10]Makosza M., Bialecki M., Nitroarylamines via the vicarious nucleophilic substitution of hydrogen: amination, alkylamination and arylamination of nitroarenes with sulfenamides. J. Org. Chem.,1998,633: 4878-4888.
[11]Schmidt R. D., Mitchell A. R., Pagoria P. F., New synthesis of TATB process development.29th International Annual Conference of ICT, Karlsruhe, Germany, 2000.
[12]Schmidt R. D., Mitchell A. R., Lee G. S., et al., New synthesis of TATB-scaleup and product charaterization. 31th International Annual Conference of ICT, Karlsruhe, Germany, 2000.
[13]Makosza M., Lemek T., Kwast A., et al. Elucidation of the vicarious nucleophilic substitution of hydrogen mechanism via studies of competition between substitution of hydrogen, deuterium, and fluorine. J. Org. Chem., 2002, 67: 394-400.
[14]Li J. S., Huang Y. G., Dong H. S., et al., Density fuctional theory study on polynitropyridines. Chinese J. Energ. Mater.,2003, 11:178-181.
[15]Li J. S., Huang Y. G, Dong H. S., Theoretical prediction of properties of polynitropyridines and their noxides. Chinese J. Energ. Mater., 2004,12:576-579.
[16]赵晓峰,刘祖亮,氨基硝基啶及其氮氧化合物的亲核取代胺化反应.应用化学2011,28(4)：376-380.
[17]Imao D., Fujihara S., Yamamoto T., et al. Efiective reductive amination of carbowl compounds with hydrogen catalyzed by iridium complex in organic solvent and in ionic liquid. Tetrahedron. 2005,61:6988-6992.
[18]罗书平,许丹倩,张帆等.离子液体中芳香醛选择性还原胺化反应研究.高等化学工程学报,2006,20：306-309.
[19]Reddy P., Kanjilal S., Sunitha S., et al. Reductive amination ofcarbonyl compounds using NaBH4 in a Bronsted acidicionic liquid. Tetrahedron Lerers.,2007, 48: 8807-8810.
[20]傅滨,李楠,梁晓梅等.还原胺化反应的新进展.有机化学,2007,27：1-7.
[21]Xu G., Ww J. R, Yang L. R., Zincborohydride-ionicliquid: stable andeficient systemforreductive reactionofaldehydeswithprimary amines to corresponding secondary amines. Chem. Res. Chinese universities.2008,24:120-122.
[22]Elizabeth R., Burkhardt R., Reductive aminationwith 5-ethy, 1-2-methylpyridineborane. Tetrahedron Lett.,2008,49:5152-5155.
[23]田兰红,张惠欣,王家喜,冯磊.功能性离子液体的合成及其在还原胺化中得应用.河北工业大学学报,2011,40：60-63.
[24]Finar, I. L., Organic Chemistry, Longman, London.1973,367.
[25]Glould E. S., Mechanism and structure in organic chemistry, Holt-dryden, New York. 1960, 291.
[26]Mocasland G. E., et al., J. Am. Chem. Soc.,1950,72:2190.
[27]Williams R., Jr. et al., Chem. Eng. News.,1955,33:3982.
[28]Leonard N. J., et al., J. Am. Chem. Soc.,1959,81:5631.
[29]王海燕,陈群,孙富安,郭一,何明阳.脂肪聚醚醇催化胺化反应的研究,化学世界,2010,9：549-551.
[30]吕璐,曹一林,马跃.化学与粘合.2003,6：300-303.
[31]刘立峰,姜志国,周亨近等.北京化工大学学报,2005,32：103-105.
[32]乔迁,长春工业大学学报,2002,23：80-82.
[33]张士福,诸勤忠,杨朝东等.CN：1635012A,[P],2005.
[34]法拉J M,哈尔肖姆B M.CN：101001902,[P],2007.
[35]郁维铭.聚氨酯工业,2002,17：1-5.
[36]Lark J. M., Renken T. L., US:4766245, [P],1988.
[37]郁维铭,张金龙,杨艳等.CN：1546550,[P],2004.
[38]陈立功,精细化工原料及中间体,2005,2：3-4.
[39]Gould, E. S., Mechanism and structure in organic chemistry, Holt-Dryden, New York, 1960,452.
[40]章思贵,精细有机化学品技术手册,科学出版社,1991,882.
[41]徐显庭,3-甲氧基丙胺的制备,上海化工,2001,13：17-19.
[42]Sabatier P., Senderens J.B., Comptes Rendus, 1905,140:482.
[43]Mignonac G, Comptes Rendus.,1920, 171:114.
[44]Winans C.F., Adkins H., J. Am. Chem. Soc., 1932,54:306.
[45]Juday R., Adkins H., J. Am. Chem. Soc., 1955,77:4559.
[46]Jiang H. J., Tzou M. S., Sachtler W. M. H., Catal. Lett.,1988, 1: 99.
[47]Feeley J., Sachtler W.M.H.,J. Catal.,1991,131:573.
[48]TrevinAo H., Sachtler W. M. H., Catal. Lett.,1994,27:251.
[49]Chatterje A., Shaikh R. A., Raj A., SingA. P. H, Catal. Lett.,1995,31:301.
[50]Hochard F, Jobic H., Massardier J., Renouprez A. J., J. Mol. Catal. A.1995,95:165.
[51]Barrault J., Pouilloux Y, Catal. Today.1997,37:137.
[52]Rode C. V., Arai M., Shirai M., Nishiyama Y., Appl. Catal.,1997,148:405.
[53]Cabello F. M., Tichit D., Coq B., Vaccari A., Dung N. T., J. Catal.,1997,167:142.
[54]Huang Y, Sachtler W. M. H., Applied Catalysis A, 1999, 182:365-378.