β-甲基戊二酸的合成及二元羧酸选择性单酯化的研究
摘要
β-甲基戊二酸即为3-甲基戊二酸、甲基戊二酸，是一种重要的医药、精细化工中间体。其单酯也广泛应用于制药工业。因此，本文不仅对β-甲基戊二酸的合成工艺进行了研究，也对其单酯化的合成工艺做了创新性研究，并延伸到一系列二元羧酸单酯化的系统研究，取得了较好的研究成果。
首先，β-甲基戊二酸的合成工艺：以氰乙酸乙酯为起始原料，经氨解反应、加成缩合反应和水解脱羧反应三步合成了β-甲基戊二酸，总收率为77%。对各步反应条件做了优化，开发了一条原料易得、操作简单、收率高、溶剂可循环使用、环境污染小的β-甲基戊二酸合成工艺路线，适于批量生产。采用间接法通过GC-MS分析了水解脱羧反应得到的β-甲基戊二酸和所含杂质，从而探讨了该反应的机理。
第二，二元羧酸单酯化的合成工艺：获得了一条绿色环保、适用性强、选择性高的合成工艺路线。最佳工艺条件为： V溶剂: m二元羧酸=2:1、n二元羧酸: m强酸性阳离子树脂=1:10、选择性都在90%以上。
最后，用红外光谱、气-质谱、核磁共振氢谱等检测方法验证了中间体及产品的结构。
β-methylglutaric acid,3-methylglutaric acid, methylglutaric acid, is an importantcuratorial and fine chemical intermediate. Methyl β-methylglutarate have a very widerange of applications in pharmaceutical industry. Therefore, in this paper the method ofsynthesis of β-methylglutaric acid, methyl β-methylglutarate were optimized, then themethod of methyl β-methylglutarate was also applied in other dicarboxylic acids. At lastachieved a good result.
Firstly, Optimization of synthesis of β-Methylglutaric acid: β-Methylglutaric acidwas synthesized through three steps of ammonolysis, addition-condensation,hydroxylation-decarboxylation by using ethyl cyanoacetate as a raw material, theoverall yield was77%. Conditions of every step was optimized. The process is easy togain materials, simple operation, high yield, solvent reusing, low environmentalpollution and suitable to scale production. The product and by-product ofhydroxylation-decarboxylation were analysed using indirect method by GC-MS and thepossible mechanism was discussed.
Second, optimization of monoesterification of dicarboxylic acids: the process isgreen environmental protection, stronger applicability and selectivity. The best craft ofselectivity mono-esterification is Vsolvent:mdicarboxylic acids=2:1, ndicarboxylic acid:mstorng-acid cationexchange resin=1:10, selectivity was above90%.
The structures of inter-mediate and production are confirmed by IR, GC-MS,1H-NMR.
首先，β-甲基戊二酸的合成工艺：以氰乙酸乙酯为起始原料，经氨解反应、加成缩合反应和水解脱羧反应三步合成了β-甲基戊二酸，总收率为77%。对各步反应条件做了优化，开发了一条原料易得、操作简单、收率高、溶剂可循环使用、环境污染小的β-甲基戊二酸合成工艺路线，适于批量生产。采用间接法通过GC-MS分析了水解脱羧反应得到的β-甲基戊二酸和所含杂质，从而探讨了该反应的机理。
第二，二元羧酸单酯化的合成工艺：获得了一条绿色环保、适用性强、选择性高的合成工艺路线。最佳工艺条件为： V溶剂: m二元羧酸=2:1、n二元羧酸: m强酸性阳离子树脂=1:10、选择性都在90%以上。
最后，用红外光谱、气-质谱、核磁共振氢谱等检测方法验证了中间体及产品的结构。
β-methylglutaric acid,3-methylglutaric acid, methylglutaric acid, is an importantcuratorial and fine chemical intermediate. Methyl β-methylglutarate have a very widerange of applications in pharmaceutical industry. Therefore, in this paper the method ofsynthesis of β-methylglutaric acid, methyl β-methylglutarate were optimized, then themethod of methyl β-methylglutarate was also applied in other dicarboxylic acids. At lastachieved a good result.
Firstly, Optimization of synthesis of β-Methylglutaric acid: β-Methylglutaric acidwas synthesized through three steps of ammonolysis, addition-condensation,hydroxylation-decarboxylation by using ethyl cyanoacetate as a raw material, theoverall yield was77%. Conditions of every step was optimized. The process is easy togain materials, simple operation, high yield, solvent reusing, low environmentalpollution and suitable to scale production. The product and by-product ofhydroxylation-decarboxylation were analysed using indirect method by GC-MS and thepossible mechanism was discussed.
Second, optimization of monoesterification of dicarboxylic acids: the process isgreen environmental protection, stronger applicability and selectivity. The best craft ofselectivity mono-esterification is Vsolvent:mdicarboxylic acids=2:1, ndicarboxylic acid:mstorng-acid cationexchange resin=1:10, selectivity was above90%.
The structures of inter-mediate and production are confirmed by IR, GC-MS,1H-NMR.
引文
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[2] W. Brzyska, W. O. ga. Spectrial and thermal studiels of rare earth element of3-me-thylglutarates[J]. Journal of Thermal Analysis and Calorimetry.2000,60:123-130.
[3] Saitou Hidekazu, Tokito Yasuo.Production of3-methylglutaric acid[P]. JP7258148,1995,10,9.
[4]朱广淑,王燕,王集会.麝香酮中间体-β-单酯工艺改进[J].山东医药工业,2002,22:47-49.
[5]孙志忠,孙野,郭乙杰,等. β-甲基戊二酸的合成工艺优化[J].化学研究与应用,2011,8:15-20.
[6]刘宪华,王本晓,王俐. β-甲基戊二酸单甲酯的制备[J].山东医药工业,2003,23:1-2.
[7] S. M. McElvain, Robert E. Kent. β-methylglutaric acid[J]. Organic Synthses,1943,23:60-67.
[8]杨文玲,康文通,李景生.三聚乙醛解聚制备乙醛研究[C].《第九届全国化学工艺学术年会论文集》,2005,7:2077-2079.
[9] James Nelson Edmund Day, Jocelyn Field Thorpe. The Formation and Reactions ofIminocompounds.Part XX.The Condensatiora of Aldehydes with Cyanoacetarnid[J].J. Chem. Soc.1920,117:1465-1468.
[10] Kan Wang, Katrina Nguyen, Yijun Huang, etal. Cyanoacetamide MulticomponentReaction (I): Parallel Synthesis Of Cyanoacetamides[J]. J. Comb. Chem.2009,11:920–927.
[11]龚美义.普瑞巴林的合成[J].广东化工,2009,36:1129-1132.
[12]蔡启祥,李临生,兰云军.二羧酸单甲酯盐的制备及其在铬鞣中的应用研究[J].皮革科学与工程,2002,2:36-40.
[13]兰翠玲,蒙衍强,赵临远.新方法合成丁二酸单甲酯的研究[J].广西师范大学学报(自然科学版),2000,18:66-68.
[14]薛海鹏,李湘洲,旷春桃,等.富马酸单戊酯与富马酸单异戊酯的合成研究[J].食品科技,2010,35:7-12.
[15]邢国秀.淀粉二元酸单酯类衍生物的合成与应用研究[D].中国科学院上海冶金研究所,2000.
[16]杜伟志.己二酸的低温快速单酯化[J].应用科学学报,1987,5:92-94.
[17] Hitoshi Kurihara, Toshio Fuchigami, Toshiki Tajima. Kolbe Carbon-Carbon Coup-ling Electrosynthesis Using Solid-Supported Bases[J]. J. Org. Chem.2008,73:6888-6890.
[18]唐嘉英,李鑫,应汉杰.离子交换树脂吸附TPS的热力学和动力学研究[J].南京工业大学学报,2006,29:79-83.
[19]余娟,黎卫亮,李梦耀,等. HDX-8树脂对2,4-二氯苯酚吸附的研究[J].应用化工,2008,7:1078-1092.
[20] Pushparathinam Gopinath, Surapaneni Nilaya, Kannoth Manheri Muraleedharan.Highly Chemoselective Esterification Reactions and Boc/THP/TBDMS Discrimin-ating Deprotections under Samarium(III) Catalysis[J]. Organic Letter,2011,8:1932-1935.
[21] Clliarle S, Ratto M, Rovatti M. Mercury removal from water by ion exchangeresins adsorption[J]. Water Research,2000,34:2971-2978.
[22] Gulay B, Begum A, Yakup M. Adsorpotion kinetics and thermodynamicParameters of cationic dyes from aqueous solutions by using a new strongcation-exchange resin[J]. Chemical, Engineering Journal,2009,152:339-346.
[23] Haruo Ogawa, Teiji Chihara, Kazuo Taya. Selective Monomethyl Esterification ofDicarboxylic Acids by use of Monocarboxylate Chemisorption on Alumina[J].J. Am. Chem. Soc.,1985,107:1365-1369.
[24] H. Ogawa, Y. Ichimura, T. Chihara. Teratani and K. Taya. Methylation of Alcohol,Phenols, and Carboxylic Acids, and Selective Monomethylation of Diols andDicarboxylic Acid with Dimethyl Sulfate by Use of Alumina[J]. Bull. Chem. Soc.Jpn.,1986,59:2481-2490.
[25]边延江,秦英,肖立伟,等. Knoevenagel缩合反应研究的新进展[J].有机化学,2006,6:1165-1172.
[26] Chattopadhyay, Sharma A. Lipase catalysed acetylation of carbohydrates[J]. Biote-ch. Lett.,1993,15:1145-l146.
[27] A. Sharma, S. Chattopadhyay, V. R. Mamdapur. PPL catalyzed monoesterificationof α,ω-dicarboxylic acids[J]. Biotechnology Letters,1995,17:939-942.
[28]李建芬,陈红梅. Knoevenagel法合成肉桂酸及其工艺优化[J].精细石油化工,2007,24:34-37.
[29] Xinsheng Li, Qianchang Ding, Jianfeng Ge. A Convenient Synthesis of (S)-H4-BI-NOL and Its Derivatives via Hydrogenation of Monoesters of BINOL[J]. J. Org.Chem.2009,74:1785-1787.
[30] A. Sharma, S. Chattopadhyay, V. R. Mamdapur. PPL catalyzed monoesterificationof α,ω-dicarboxylic acids[J]. Biotechnology letters,1995,17:939-942.
[31] Stephan M. Levonis, Laurent F. Bornaghi, Todd A. Houston. Selective Monoest-erification of Malonic Acid Catalyzed by Boric Acid[J]. Aust. J. Chem.,2007,60:821-823.
[32] Takeshi Nishiguchi, Yasuhiro Ishii, Shizuo Fujisaki. Selective monoesterificationof dicarboxylic acids catalysed by ionexchange resins[J]. J. Chem. Soc., PerkinTrans.,1999,1:3023-3027.
[33] Meenakshi S, Natrayasamy Viswanathan. Identification of selective ion-exchangeresin for fluoride sorption[J]. Colloid and Interface Science,2007,308:438-450.
[34] Tian Wenyu, Zeng Zuoxiang, Xue Weilan. Kinetics of the Mono-esterification Be-tween Terephthalic Acid and1,4-Butanediol[J]. Chinese Journal of Chemical Engi-neering,2010,18:391-396.
[35] G. Bayramoglu, M.Y. Arica. Kinetics of mercury ions removal from synthetic aqu-eous solutions using by novel magnetic p(GMA-MMA-EGDMA) beads[J].Hazard.Mater.2007,144:449-457.
[36] Li-Ming Zhu. Applications of pig liver esterases (PLE) in asymmetric sythesis[J].Tetrahedron,1996,46:6587-6611.
[37] F. Ancillotti, M. M. Mauri, E. Pescarollo. Ion exchange resin catalyzed addition ofalcohols to olefins[J]. Catal.,1977,46:49-56.
[38] S. S. Jayadeokar, M. M. Sharma. Ion exchange resin catalysed etherification of eth-ylene and propylene glycols with isobutylene[J]. React. Polym.,1993,20:57-60.
[39] S. K. Ghosh, M. M. Sharma. Separation of close-boiling phenols and naphthols thr-ough their selective etherification with isobutylene/isoamylene: Acidic ionexchange resin as catalyst[J]. React. Polym.,1992,16:159-167.
[40] Anon.. Ion Exchange: A new sphere of action[J]. Chem. Eng.,1992,99:63-80.
[41] S. S. Bhagade, G. D. Nageshwar. Catalysis by ion exchange resins Hydration[J].C-hem. Petro Chem. J.,1981,12:21-32.
[42] Gulay Bayramoglu, Begum Altintas, M. Yakup Arica. Adsorption kinetics and the-rmodynamic parameters of cationic dyes from aqueous solutions by using a new st-rong cation-exchange resin[J]. Chemical Engineering Journal,2009,152:339-346.
[43] Auwers, Kobner, von Meyenburg. LXXXI.-Constitutioiz of Ethyl Sodiocyurmceta-te and of Ethyl Sodiomethylcyanacetate[J]. Ber.,1891,24:923-936.
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