固体酸催化合成氨基酸酯的工艺研究
摘要
氨基酸酯的合成是近年来迅速发展起来的一个新研究领域,它在医药、化工、食品、农业等方面有着越来越广泛的应用,可用作药物中间体、食品添加剂、化妆品添加剂和杀菌灭虫合剂等,应用前景十分广阔。研究开发工艺可靠、成本合理的氨基酸酯制备技术具有重要的理论和实际意义。
固体酸催化剂具有活性高、选择性好、不腐蚀设备、不污染环境等优点,被认为是未来氨基酸酯化反应的首选催化剂。离子交换树脂作为固体酸催化剂的一个门类,已被广泛的应用到有机合成中,而在酯化过程中,用微波辐射替代传统加热方式,可大量节省电能,减少耗水量,同时反应周期大幅度缩短,可以从根本上降低生产成本。
本论文对氨基酸酯的合成工艺进行了研究,工作主要包括以下几方面:
从6种常见的强酸性苯乙烯系阳离子交换树脂中筛选出催化活性最高的树脂作催化剂,直接酯化合成游离的苯丙氨酸异戊酯,研究各种因素对酯化反应的影响,优化了产品的分离提纯条件,并考察了催化剂的稳定性。同时对阳离子交换树脂催化合成氨基酸酯的机理进行了初步的探讨。
用筛选出的催化活性最高的D061大孔型强酸性阳离子交换树脂做催化剂合成一系列游离的氨基酸异丙酯、异丁酯和异戊酯。同时通过红外光谱、核磁共振氢谱确定了最终产品的化学结构。讨论了带水剂对反应时间和产率的影响,对制备不同氨基酸酯的回流温度和酯化收率的差异进行了分析。
用Discover微波反应器替代传统加热方式,制备了一系列氨基酸异丙酯和氨基酸异丁酯,对微波反应条件进行研究,优化了微波合成游离氨基酸酯的工艺,并与常规加热方法进行了比较,归纳总结了它们的优缺点。
Amino acids esters, of which the synthesis has rapidly become a new research field in recent years, have been extensively used as medical semi-product, food additives, cosmetic additives, mineral flotation assitives, germicides, etc. So resesrch on the synthesis of amino acids esters is of great significance both in theoretical and in practical side.
Solid acid catalyst has a lot of advantages, such as high activity, good selectivity, no corrosion to equipments and preventing acid wastewater from draining off, etc. It is considered as the first choice catalysts of amino acid easterification in the future. Ion exchange resin which is a kind of solid acid catalyst, has been widely applied to organic synthesis. Microwave irridation is introduced instead of traditional heating in the synthesis can save energy, save water, greatly shorten reaction cycle, so the production cost can be decreased radically.
Preparation technologies of a series of amino acids esters have been studied systematically, and it contains several aspects:
Free phenylalanine isoamyl ester has been synthesized from L-phenylala-nine and isoamyl alcohol by direct esterification with resin as catalyst which is the most effective of six familiar strong acidic cation exchange resins. The influentical factors have been studied and optimized. After three successive experiments, activity and capacity of the catalyst remains on the initial level indicating good stability. And the mechanism of esterifition of amino acid using strong acid resin as catalyst has been primarily dicussed.
A series of free Amino acid isopropyl ester, Amino acid isobutyl ester and Amino acid isoamyl ester have been synthesized by direct esterification with D061 resins as catalyst which is the most effective of six familiar strong acidic cation exchange resins. Final products have been characterized by IR,1HNMR. The effect of dehydrating reagents on reaction time and the yield of esterification has been investigated. The differences of reflux temperature and the yield of esteri-fication on the synthesis of various amino acid ester have been analyzed.
Microwave irridation has been introduced instead of traditional heating in the synthesis of a series of free Amino acid isopropyl ester and Amino acid isobutyl ester. The effects of microwave irradiation power and reaction time on esterification reaction have been discussed. The synthesis processe of amino acid ester has been optimized. Theses two technologies have been analyzed summarized.
固体酸催化剂具有活性高、选择性好、不腐蚀设备、不污染环境等优点,被认为是未来氨基酸酯化反应的首选催化剂。离子交换树脂作为固体酸催化剂的一个门类,已被广泛的应用到有机合成中,而在酯化过程中,用微波辐射替代传统加热方式,可大量节省电能,减少耗水量,同时反应周期大幅度缩短,可以从根本上降低生产成本。
本论文对氨基酸酯的合成工艺进行了研究,工作主要包括以下几方面:
从6种常见的强酸性苯乙烯系阳离子交换树脂中筛选出催化活性最高的树脂作催化剂,直接酯化合成游离的苯丙氨酸异戊酯,研究各种因素对酯化反应的影响,优化了产品的分离提纯条件,并考察了催化剂的稳定性。同时对阳离子交换树脂催化合成氨基酸酯的机理进行了初步的探讨。
用筛选出的催化活性最高的D061大孔型强酸性阳离子交换树脂做催化剂合成一系列游离的氨基酸异丙酯、异丁酯和异戊酯。同时通过红外光谱、核磁共振氢谱确定了最终产品的化学结构。讨论了带水剂对反应时间和产率的影响,对制备不同氨基酸酯的回流温度和酯化收率的差异进行了分析。
用Discover微波反应器替代传统加热方式,制备了一系列氨基酸异丙酯和氨基酸异丁酯,对微波反应条件进行研究,优化了微波合成游离氨基酸酯的工艺,并与常规加热方法进行了比较,归纳总结了它们的优缺点。
Amino acids esters, of which the synthesis has rapidly become a new research field in recent years, have been extensively used as medical semi-product, food additives, cosmetic additives, mineral flotation assitives, germicides, etc. So resesrch on the synthesis of amino acids esters is of great significance both in theoretical and in practical side.
Solid acid catalyst has a lot of advantages, such as high activity, good selectivity, no corrosion to equipments and preventing acid wastewater from draining off, etc. It is considered as the first choice catalysts of amino acid easterification in the future. Ion exchange resin which is a kind of solid acid catalyst, has been widely applied to organic synthesis. Microwave irridation is introduced instead of traditional heating in the synthesis can save energy, save water, greatly shorten reaction cycle, so the production cost can be decreased radically.
Preparation technologies of a series of amino acids esters have been studied systematically, and it contains several aspects:
Free phenylalanine isoamyl ester has been synthesized from L-phenylala-nine and isoamyl alcohol by direct esterification with resin as catalyst which is the most effective of six familiar strong acidic cation exchange resins. The influentical factors have been studied and optimized. After three successive experiments, activity and capacity of the catalyst remains on the initial level indicating good stability. And the mechanism of esterifition of amino acid using strong acid resin as catalyst has been primarily dicussed.
A series of free Amino acid isopropyl ester, Amino acid isobutyl ester and Amino acid isoamyl ester have been synthesized by direct esterification with D061 resins as catalyst which is the most effective of six familiar strong acidic cation exchange resins. Final products have been characterized by IR,1HNMR. The effect of dehydrating reagents on reaction time and the yield of esterification has been investigated. The differences of reflux temperature and the yield of esteri-fication on the synthesis of various amino acid ester have been analyzed.
Microwave irridation has been introduced instead of traditional heating in the synthesis of a series of free Amino acid isopropyl ester and Amino acid isobutyl ester. The effects of microwave irradiation power and reaction time on esterification reaction have been discussed. The synthesis processe of amino acid ester has been optimized. Theses two technologies have been analyzed summarized.
引文
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[9] TAO Y K, HE H G. Method for Producing Ionic Liquid of Amino Acid Ester Cation: CN, 1621152[P]. 2005.
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[12] MIRVISS S B, DAHOD S K, Empie M W. Synthesis of L-Phenylalanine Meth-yl Ester[J]. Eng. Chem. Res, 1990, 29: 651-659.
[13]陈帆.新型手性氨基酸衍生物及其合成方法与应用: CN, 1616411[P]. 2005.
[14]冯光炷,朱春山,王晓君,等.复合氨基酸月桂醇酯的合成及性能[J].郑州工程学院学报, 2004, 24(4): 42-45.
[15]王钝,梁益衡,宫平,等.抗糖尿病药物那格列奈的合成[J].中国药物化学杂志. 2005, 12(2): 94-96.
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[19]龙姝,陈敏,莫文妍,等. N-[甲氧(乙氧)羰基亚甲基]-5-取代苯基-2E, 4E-戊二烯酰胺的合成与生物活性研究[J].华中师范大学学报(自然科学版), 2002, 36(2): 185-187.
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[27] SATO, HARUYO, TAKAE, et al. Optically Active Amino Acid Benzyl Esters and Processes for The Preparation of the Same:JP, 74920000210[P]. 2000.
[28]安广杰,王璋,许时婴.蛋氨酸烷基酯的合成[J].食品添加剂, 2004, 25(12): 107-108.
[29] MILLER H, AELSCH H. Benzyl Esters of Amino Acids[J]. Am. Chem. Soc, 1952, 74: 1092-1093.
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[32] RIVERO A, HEREDIA S, OCHOA A. Esterification of Amino Acids and Mono Acids Using Triphosgene[J]. Synthetic Communications, 2005, 31(14): 2169-2175.
[33] KOZODZIFJCZYK A M, SLEBJODA M. A Rapid Procedure for the Esterifica- tion of Amino Acids[J]. Systhesis Communications, 1984, 865-866.
[34] ANAND R C, VIMAL. A Mild and Convenient Procedure for the Esterification of Amino Acid[J]. Synthetic Communications, 1998, 28(11): 1963-1965.
[35] ZANDER N, FRANK R. Polystyrylsulfonyl Chloride Resin: an Efficient Solid-supported Condensation Reagent for the Solution Phase Synthesis of Esters[J]. Tetrahedron.Lett, 2001, 42(44): 7783-7785.
[36] SIEBER P. An Improved Method for Anchoring of 9-Fluorenylmethoxy-carbonyl-amino Acids to 4-Alkoxybenzyl Alcohol Resins[J]. Tetrahedron. Lett, 1987, 28(49): 6147-6150.
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[39] WEGMAN A M, ELZINGA M J, NEELEMANAND E, et al. Salt-free Esterification ofα-Amino Acids Catalysed by Zeolite H-USY[J]. Green Chemistry, 2001, 3: 61-64.
[40] KISE H, SHIRATO H. Synthesis of Aromatic Amino Acid Ethyl Esters byα-Chymotrypsin in Solutions of High Ethanol Concentrations[J]. Tetrahedron. Lett, 1985, 26(49): 6081-6084.
[41] CHEN S T, WANG K T. Papain Catalysed Esterification of N-Protected Amino Acids[J]. Chem. Commun, 1988: 327-329.
[42] YESILOGLUL Y, KILIC I. Polyvinyl Alcohol-trypsin as a Catalyst for Amino Acid Ester Synthesis in Organic Media[J]. Preparative Biochemistry & Biotech-nology, 2004, 34(4): 365-375.
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[2] SCHRIDER E, LUBKE K. The Peptides[J]. Academic Press, 1965: 52-75.
[3] BRUGGINK A.Penicillin Acylase in the Industrial Production ofβ-Lactam Antibiotics[J]. Org. Process Res. Dev. (Review), 1998, 2(2): 128-133.
[4] HOUNG J, WU M L, CHEN S T. Kinetic Resolution of Amino Acids Esters Catalyzed by Lipases[J]. Chirality, 1996, 8: 418-422.
[5] AMATO D, WELLINGTON F. Amino Acid Esters as Nutrient Supplements and Methods of Use: US, 0148669[P]. 2005-04-29.
[6] DESHAYES S, LIAGRE M, LOUPY A, et al. Microwave Activation in Phase Transfer Catalysis[J]. Tetrahedron, 1999, 55: 10851-10870.
[7] LIDSTROM P, TIERNEY J, WATHEY B, et al. Microwave Assisted Organic Synthesis a Review[J]. Tetrahedron, 2004, 57: 9225-9283.
[8] AMATO D, WELLINGTON L F. Amino Acid Esters as Nutrient Supplements and Methods: US, 0148669[P]. 2005.
[9] TAO Y K, HE H G. Method for Producing Ionic Liquid of Amino Acid Ester Cation: CN, 1621152[P]. 2005.
[10] SACHS H, BRAND E. Benzyl Esters of Glutamic Acid[J]. Amer. Chem. Soc, 1953, 75(18): 4610-4611.
[11] AJIOKA, MASANOBU, HIGUCHI, et al. Preparation and Isolation of Mineral Acid Salt of an Amino Acid Methyl Ester: EP, 0376230[P]. 1989.
[12] MIRVISS S B, DAHOD S K, Empie M W. Synthesis of L-Phenylalanine Meth-yl Ester[J]. Eng. Chem. Res, 1990, 29: 651-659.
[13]陈帆.新型手性氨基酸衍生物及其合成方法与应用: CN, 1616411[P]. 2005.
[14]冯光炷,朱春山,王晓君,等.复合氨基酸月桂醇酯的合成及性能[J].郑州工程学院学报, 2004, 24(4): 42-45.
[15]王钝,梁益衡,宫平,等.抗糖尿病药物那格列奈的合成[J].中国药物化学杂志. 2005, 12(2): 94-96.
[16] YAMAMOTO, YASUHITO. Process for Production of Optically Active (R or S)-Amino Acid or Optically Active (R or S)-Amino Acid Ester: WO, 20070239 48[P]. 2007.
[17] PATEL R P, PRICE S. Synthesis of Benzyl Esters of a Amino Acids[J]. Org. Chem, 1965, 30(10): 3575-3576.
[18]思洋,刘乐乐,张廓,等.氨基酸甲乙酯的合成及纯化[J].内蒙古医学院学报, 2005, 27(1): 33-34.
[19]龙姝,陈敏,莫文妍,等. N-[甲氧(乙氧)羰基亚甲基]-5-取代苯基-2E, 4E-戊二烯酰胺的合成与生物活性研究[J].华中师范大学学报(自然科学版), 2002, 36(2): 185-187.
[20] BOEDTEN, WIHELMUS, HUBERTUS, et al. Prosess for Esterification of Amino Acids and Peptides: WO, 9849133[P]. 1998.
[21] ZHAO H, MALHOTRA S V. Esterification of Amino Acids by Using Ionic Liquid as a Green Catalyst[J]. Chemical Industries, 2004, 89: 667-672.
[22] ERLANGER B F, HALL R M. Improved Synthesis of Amino Acid Benzyl Esters [J]. Amer. Chem. Soc, 1954, 76: 5781-5782.
[23] ARAI I, MURAMATSU I. A Simple and Convenient Method for Esterification of Tryptophan and Other Amino Acids[J]. Org. Chem, 1983, 48: 121-123.
[24] MACLAREN J A, SAVIGE W E, SWAN J M. Amino Acids and Peptides. IV. Intermediates for the Synthesis of Certain Cystine-Containing Peptide Sequence in Insulin[J]. Australian Journal of Chemistry, 1958, 11: 345-599.
[25] ROESKE R. Preparation of t-Butyl Esters of Free Amino Acids[J]. Org. Chem, 1963, 28(5): 1251-1253.
[26] ABODERIN A A, DELPIERRE G R, FRUTON J S. Benzhydryl Esters of Amino Acids in Peptide Synthesis[J]. Amer. Chem. Soc, 1965, 87(23): 5469-5472.
[27] SATO, HARUYO, TAKAE, et al. Optically Active Amino Acid Benzyl Esters and Processes for The Preparation of the Same:JP, 74920000210[P]. 2000.
[28]安广杰,王璋,许时婴.蛋氨酸烷基酯的合成[J].食品添加剂, 2004, 25(12): 107-108.
[29] MILLER H, AELSCH H. Benzyl Esters of Amino Acids[J]. Am. Chem. Soc, 1952, 74: 1092-1093.
[30] SHIELDS J E, MCGREGOR H, CARPENTER F H. Preparation of Benzyl and p-Nitrobenzyl Esters of Amino Acids[J]. Org. Chem, 1961, 26: 1491-1494.
[31] PENNEY C L, SHAH P, LANDI S. A Simple Method for the Synthesis of Long-chain Alkyl Esters of Amino Acids[J]. Org. Chem, 1985, 50: 1457-1459.
[32] RIVERO A, HEREDIA S, OCHOA A. Esterification of Amino Acids and Mono Acids Using Triphosgene[J]. Synthetic Communications, 2005, 31(14): 2169-2175.
[33] KOZODZIFJCZYK A M, SLEBJODA M. A Rapid Procedure for the Esterifica- tion of Amino Acids[J]. Systhesis Communications, 1984, 865-866.
[34] ANAND R C, VIMAL. A Mild and Convenient Procedure for the Esterification of Amino Acid[J]. Synthetic Communications, 1998, 28(11): 1963-1965.
[35] ZANDER N, FRANK R. Polystyrylsulfonyl Chloride Resin: an Efficient Solid-supported Condensation Reagent for the Solution Phase Synthesis of Esters[J]. Tetrahedron.Lett, 2001, 42(44): 7783-7785.
[36] SIEBER P. An Improved Method for Anchoring of 9-Fluorenylmethoxy-carbonyl-amino Acids to 4-Alkoxybenzyl Alcohol Resins[J]. Tetrahedron. Lett, 1987, 28(49): 6147-6150.
[37] MENGE B B, NIMTZ M, FRANK R. An Efficient Method for Anchoring Fmoc-anino Acids to Hydroxyl-functionalised Solid Supports[J]. Tetrahedron. Lett, 1990, 31(12): 1701-1704.
[38] ZANDER N, GERHARDT J, FRANK R. Polystyrylsulfonyl-3-nitro-1H-1,2,4-triazolide-resin: a New Solid-supported Reagent for the Esterification of Amino Acids[J]. Tetrahedron. Lett, 2004, 44: 6557-6560.
[39] WEGMAN A M, ELZINGA M J, NEELEMANAND E, et al. Salt-free Esterification ofα-Amino Acids Catalysed by Zeolite H-USY[J]. Green Chemistry, 2001, 3: 61-64.
[40] KISE H, SHIRATO H. Synthesis of Aromatic Amino Acid Ethyl Esters byα-Chymotrypsin in Solutions of High Ethanol Concentrations[J]. Tetrahedron. Lett, 1985, 26(49): 6081-6084.
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