吗啉及其N-烷基衍生物的合成工艺总结
Overview on the Synthesis of Morpholine and Its N-Alkyl Derivatives
DOI: 10.12677/HJCET.2017.71005, PDF, HTML, XML, 下载: 1,867  浏览: 4,354  国家自然科学基金支持
作者: 竺贝贝, 钱 超, 陈新志：浙江大学化学工程与生物工程学院，浙江省化工高效制造技术重点实验室，浙江 杭州；张 琪, 叶小明：浙江大学化学工程与生物工程学院，浙江省化工高效制造技术重点实验室，浙江 杭州；四川之江高新材料股份有限公司，四川 遂宁；施锁连：四川之江高新材料股份有限公司，四川 遂宁
关键词: 有机胺；醚化；胺化；N-烷基化；Amine； Etherification； Amination； N-Alkylation
摘要: 吗啉及其N-烷基衍生物是重要的精细化工中间体，已广泛应用于橡胶、医药与农药等领域。本文根据吗啉及其N-烷基衍生物的结构特点，将其合成方法概括为：C-O-C键合的醚化法、C-N-C键合的仲胺化法和N-烷基化法，分析了各种方法的工艺特点，并指出了吗啉及其N-烷基衍生物合成工艺的发展趋势。
Abstract: Morpholine and its N-Alkyl derivatives are a class of important intermediates for many fine chemicals, which have been widely used in rubber, medicine, pesticide and other fields. This paper summarized several methods to synthetize these compounds according to their structural characteristics: the etherification of C-O-C bond linkage, the amination of C-N-C bond linkage and the N-alkylation of morpholine. The features of each method were analyzed. Finally, the development in the synthesis technology of morpholine and its N-alkyl derivatives was proposed.
文章引用：竺贝贝, 张琪, 施锁连, 叶小明, 钱超, 陈新志. 吗啉及其N-烷基衍生物的合成工艺总结[J]. 化学工程与技术, 2017, 7(1): 31-37. http://dx.doi.org/10.12677/HJCET.2017.71005

参考文献

[1] 王勋章, 田振生. 吗啉国内外现状及发展前景[J]. 化工科技, 2005, 13(5): 63-67.
[2] Xue, S. (2011) The Properties of Morpholine and Its Application in Metalworking Lubricant. Lubrication Engineering, 36, 116-118.
[3] 邢鹏, 王勇, 陈立功. 吗啉衍生物的合成研究[J]. 化学工业与工程, 2003, 20(6): 347-350.
[4] Kozin, V.G. and Mukhamadiev, A.A. (2001) Dissolving and Selective Properties of Morpholine-Based Mixed Solvents. Russian Journal of Applied Chemistry, 74, 1289-1294. https://doi.org/10.1023/A:1013798011256
[5] Subramanian, A., et al. (1998) Morpholine and Its Derivatives as Vapor Phase Corrosion Inhibitors for Mild Steel. Bulletin of Electrochemistry, 14, 289-290.
[6] 薛绍玲, 薛中. 吗啉的性能及其在金属加工液中的应用[J]. 润滑与密封, 2011, 36(2): 118-119.
[7] 蔡映杰, 林丽娜, 李进, 等. N-甲基吗啉-N-氧化物去除苎麻残胶研究[J]. 印染助剂, 2011, 28(9): 36-38.
[8] 梁诚. 我国橡胶助剂原料的生产现状与发展趋势[C]//中国橡胶工业协会. 全国橡胶工业新材料技术交流会暨2003年橡胶助剂专业委员会会员大会论文集: 2004年卷. 桂林, 2003: 11-31.
[9] 高树藩, 王田君, 王丽, 等. N-烷基吗啉的合成[J]. 化学通报, 1998(3): 30-33.
[10] 韩秀山. 吗啉的应用及生产科研概况[J]. 化工中间体网刊, 2002, 5(5): 33-36.
[11] 赵丽梅, 王秉臣, 何少文. 吗啉的生产应用及市场分析[J]. 化工中间体, 2005(10): 11-14.
[12] 李春生, 刘华彦, 周春晖,等. 吗琳的合成方法及工艺评述[J]. 浙江化工, 2002(1): 14-16.
[13] 李正西. 吗啉的生产路线和国内生产概况[J]. 当代石油石化, 1996(3): 39-40.
[14] 陈汉庚, 张涛, 罗明,等. Cu-Ni-Co/Al2O3气固相催化合成N-甲基吗啉[J]. 高校化学工程学报, 2009, 23(5): 801- 806.
[15] 张龙传, 邹纪丞. 国内吗啉生产工艺现状[J]. 中国石油和化工, 2007(9): 56-59.
[16] Bukala, M., Witek, S. and Bogdal, S. (1977) N-Alkylmorpholine from Alkyldiethanolamine. PL Patent No. 83092.
[17] 陈新志, 竺贝贝, 叶小明, 等. N-甲基吗啉的循环制备法[P]. 中国专利, 201611073210.9. 2016-11-07.
[18] Petro, M., Mravec, D. and Ilavsky, J. (1983) Kinetics of Esterification of 1-Pentanol by Isobutyric Acid and Benzyl Alcohol by Acetic-Acid. Chemicke Zvesti, 37, 461-466.
[19] Steven, H.V. and Robert, L.Z. (1987) Catalytic Method for the Manufacture of N-Alkylmorpholines. US Patent No. 4647664.
[20] Jun, L. and Wu, M.L. (2009) Advances in the Comprehensive Utilization of Diethylene Glycol. Guangzhou Chemical Industry, 37, 35-38.
[21] 王硕, 侯淑兰, 王勋章, 等. 二甘醇氨化合成1,4-氧氮杂环己烷催化剂及其工艺[P]. 中国, 1241683C. 2006-02-15.
[22] 叶小明, 张超, 陈新志, 等. N, N-二甲基二甘醇胺的合成法[P]. 中国专利, 201710010662.0. 2017-01-06.
[23] Daughenbaugh, R.J., Dixon, D.D. and Fowlkes, R.L. (1981) Sythesis of Morpholine and Derivatives There of via the Reaction of Dialkylene Glycol and Ammonia. EP Patent No. 0036331.
[24] Schroeder, W.D. and Lengsfeld, W.D. (1985) Process and Catalyst for the Preparation of Cyclicimines. DE Patent No. 3125662.
[25] 赵淑梅, 张福康. N-甲基吗啉合成工艺的研究[J]. 精细化工, 1999, 16(3): 63-64.
[26] 田怀广. 吗啉的技术进展和市场前景[J]. 安徽化工, 2001(6): 19-20.
[27] Mesropyan, E.G., et al. (2005) New Morpholine Defivmives. Khimiya Geterotsikl-icheskikh Soedinenii, 11, 1691-1692．
[28] 张想竹, 张继昌, 吴明书. N-甲基吗啉的合成[J]. 应用化学, 2003, 20(9): 917-918.
[29] Khan, K.M., et al. (2009) Leishmanicidal Potential of N-Substituted Morpholine Derivatives: Synthesis and Structure-Activity Relmionships. Natural Product Research, 23, 479-484. https://doi.org/10.1080/14786410802090359
[30] 张想竹, 吴明书. N-甲基吗啉的合成研究[J]. 精细石油化工, 2002(4): 4-5.
[31] Alinezhad, H., Tajbakhsh, M. and Zamani, R. (2006) Efficient and Mild Procedure for Reductive Methylation of Amines Using N-Methylpiperidine Zinc Borohydride. Synthetic Communications, 36, 3609-3615. https://doi.org/10.1080/00397910600943667
[32] Delzotto, A., Baratta, W., Sandri, M., Verardo, G. and Rigo, P. (2004) Cyclopentadienyl Ru II, Complexes as Highly Efficient Catalysts for the N-Methylation of Alkylamines by Methanol. European Journal of Inorganic Chemistry, 2004, 524-529. https://doi.org/10.1002/ejic.200300518
[33] Chen, X.Z., Luo, H., Qian, C. and He, C. (2011) Research on the N-Alkylation of Morpholine with Alcohols Catalyzed by CuO-NiO/γ-Al2O3. Reaction Kinetics, Mechanisms and Catalysis, 104, 163-171. https://doi.org/10.1007/s11144-011-0325-0
[34] Jiratova, K., Solcova, O., Snajdaufova, H., Moravkova, L. and Zahradnikova, H. (1993) Reductive Amination of Diethylene Glycol to Morpholine on Supported Nickel Catalysts—Its Activity, Selectivity, Stability and Possibility of Reactivation. Studies in Surface Science & Catalysis, 75, 1235-1245. https://doi.org/10.1016/S0167-2991(08)64447-X
[35] 李颖. 二乙醇胺脱水环化法制取吗啉工艺条件的探讨[J]. 科技情报开发与经济, 2002, 12(5): 174-175.
[36] 罗虎. 吗啉及其烷基衍生物的合成工艺研究[D]: [硕士学位论文]. 杭州: 浙江大学化工系, 2012.
[37] Mesropyan, E.G., Ambartsumyan, G.B., Avetisyan, A.A., Galstyan, A.S. and Kirakosyan, A.N. (2005) New Morpholine Derivatives. Chemistry of Heterocyclic Compounds, 41, 1424-1425. https://doi.org/10.1007/s10593-006-0013-6
[38] 黄金霞, 王宏伟, 宋长华, 等. 吗啉市场与技术进展[J]. 化学工业, 2012(9): 22-25.
[39] Wang, X.Z. and Tian, Z.S. (2005) Situation and Development Trend of Morpholine. Science and Technology in Chemical, 13, 63-67.