3，5-二甲基吡啶催化加氢反应的研究
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摘要
3,5-二甲基哌啶是合成大环内酯类新型抗菌素替米考星的重要原料。作为药物中间体,3,5-二甲基哌啶主要要求顺式构型占85%、反式构型占15%。通过3,5-二甲基吡啶加氢还原的方法是大批量获得3,5-二甲基哌啶的最佳方法。
本论文研究了不同金属催化剂对催化3,5-二甲基吡啶加氢反应的影响。考察了温度、压力、反应时间、溶剂等反应条件对3,5-二甲基吡啶加氢反应的影响。利用催化剂III在130℃,9.5 MPa,反应24 h可以得到82%的产率,非对映选择性可以达到91%。利用催化剂IV在130℃,9 MPa反应24 h可以得到92%的产率,非对映选择性可以达到70%。催化剂重复,活性和选择性无明显下降。利用两种催化剂的加氢产物的混合可以得到所需要顺反比例的产品。
另外本文以L-脯氨酸为主要原料合成了4种脯氨酸衍生的新型手性有机小分子Br?nsted酸,初步对这种催化剂的催化性能进行了研究,发现了这种催化剂对亚胺的还原反应具有良好的催化效果。
3,5-Dimethylpiperidine is an important starting material of tilmieosin, which is a semi-synthetic maerolide antibiotic developed for veterinary use. As an intermediate, 3,5-dimethylpiperidine is a mixture of 85% cis-isomer and 15% trans-isomer. Hydrog- enation of 3,5-dimethylpyridine is the best method to obtain 3,5-dimethylpiperidine.
In this thesis, catalytic activities of various metal catalysts in the hydrogenation of 3,5-dimethylpyridine were investigated. The influence of reaction parameters such as temperature, pressure, time, and solvent on the hydrogenation was investigated. Catalyst III under the optimum reaction conditions:130℃, 9.5 MPa , 24 h, ethanol as the solvent, the conversion and the diastereoselective of 3,5-dimethylpyridine could be up to 82% and 91% respectively. Catalyst IV under the optimum reaction conditions:130℃, 9 MPa, 24 h, ethanol as the solvent, the conversion and the diastereoselective of 3,5-dimethylpyridine could be up to 92% and 70% respectively. The cyclic reuse of catalysts showed that the activity and diastereoselective did not decrease significantly. Mixture of two kinds of products was consistent with the goal product.
Four proline-derived small chiral Br?nsted acids were synthesized using L-proline as the starting materials. The catalytic activity of the Br?nsted acid as organocatalyst was estimated. The results showed that the activity of these Br?nsted acids was high in the reduction of imines.
本论文研究了不同金属催化剂对催化3,5-二甲基吡啶加氢反应的影响。考察了温度、压力、反应时间、溶剂等反应条件对3,5-二甲基吡啶加氢反应的影响。利用催化剂III在130℃,9.5 MPa,反应24 h可以得到82%的产率,非对映选择性可以达到91%。利用催化剂IV在130℃,9 MPa反应24 h可以得到92%的产率,非对映选择性可以达到70%。催化剂重复,活性和选择性无明显下降。利用两种催化剂的加氢产物的混合可以得到所需要顺反比例的产品。
另外本文以L-脯氨酸为主要原料合成了4种脯氨酸衍生的新型手性有机小分子Br?nsted酸,初步对这种催化剂的催化性能进行了研究,发现了这种催化剂对亚胺的还原反应具有良好的催化效果。
3,5-Dimethylpiperidine is an important starting material of tilmieosin, which is a semi-synthetic maerolide antibiotic developed for veterinary use. As an intermediate, 3,5-dimethylpiperidine is a mixture of 85% cis-isomer and 15% trans-isomer. Hydrog- enation of 3,5-dimethylpyridine is the best method to obtain 3,5-dimethylpiperidine.
In this thesis, catalytic activities of various metal catalysts in the hydrogenation of 3,5-dimethylpyridine were investigated. The influence of reaction parameters such as temperature, pressure, time, and solvent on the hydrogenation was investigated. Catalyst III under the optimum reaction conditions:130℃, 9.5 MPa , 24 h, ethanol as the solvent, the conversion and the diastereoselective of 3,5-dimethylpyridine could be up to 82% and 91% respectively. Catalyst IV under the optimum reaction conditions:130℃, 9 MPa, 24 h, ethanol as the solvent, the conversion and the diastereoselective of 3,5-dimethylpyridine could be up to 92% and 70% respectively. The cyclic reuse of catalysts showed that the activity and diastereoselective did not decrease significantly. Mixture of two kinds of products was consistent with the goal product.
Four proline-derived small chiral Br?nsted acids were synthesized using L-proline as the starting materials. The catalytic activity of the Br?nsted acid as organocatalyst was estimated. The results showed that the activity of these Br?nsted acids was high in the reduction of imines.
引文
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[3] O. Etsuo., T. Hitoshi., H. Hiroyuki et al. Dibenz[b,e]oxepin derivatives:novel antiallergic agents possessing thromboxane A2 and histamine H1 dual antagonizing activity[J]. J. Med. Chem, 1993, 36(3): 417-420.
[4]张宏哲,吴春丽,彭宗强等.替米考星的合成[J].河南化工, 2005, 22(5): 21-22.
[5] H. Poerwono, K. Higashiyama, H. Takahashi. Stereocontrolled Syntheses of Piperidine Derivatives Using Diastereoselective Reactions of Chiral 1,3-Oxazolidines with Grignard Reagents: Asymmetric Syntheses of the Pinidine Enantiomers[J]. J. Org. Chem, 1998, 63(8):2711-2713.
[6] J. Ahman, P. Somfai. Aza-[2,3]-Wittig Rearrangements of Vinylaziridines[J]. J. Am. Chem. Soc, 1994, 116(21): 9781-9782.
[7] S. Ciblat, P. Besse, V. Papastergiou, et al. A simple and efficient enantioselective synthesis of piperidine alkaloids dihydropinidine and isosolenopsins A, B and C[J]. Tetrahedron: Asymmetry, 2000, 11(10): 2221-2229.
[8]廖代伟.催化科学导论[M].中国:化学工业, 2006: 96-97.
[9]尼可赫夫·钱德拉·巴德瓦,南赫·莱·楚瑞萨,普偌迪普·古马·沃尔马,et al.从顺式-3,5-二甲基哌啶的几何异构体中分离顺式3,5-二甲基哌啶的方法[P]. CN: 1636979A, 2004: 1-7.
[10]薛芳,林棋,林朝芬等.负载型纳米贵金属催化剂催化吡啶及其衍生物的加氢反应.催化学报, 2006, 27(10): 921-926.
[11]陈声宗,郭玉良,叶娇等.吡啶催化合成工艺研究[J].化学反应工程与工艺, 2000, 4(16): 405-407.
[12]陈声宗,黄光磊,李文生等.吡啶催化加氢制哌啶的研究[J].燃料化工, 2000, 3(31): 151-152.
[13]石卫兵,颜文革,郭彦彰等. 3-甲氨基哌啶的制备方法[P]. CN:101070303A, 2006: 1-9.
[14]杜曦,施颖,胡家元等. Ru-Pd双金属负载型催化剂对吡啶赫甲基吡啶催化加氢反应研究[J].石油化工, 2004, 33(8): 752-755.
[15]杜争鸣,周昌友,纪文富等.顺反式混合异构体3,5-二甲基哌啶的制备方法[P]. CN:101104146A, 2008: 1-6.
[16] R. Chandrashekar, Naveenkumar Kolla, et al. New Synthesis of Donepezil Through Palladium-Catalyzed Hydrogenation Approach[J]. Synthetic Communications, 2006, 36(2): 169–174.
[17]胡跃飞,程传杰,王歆燕等.一种催化氢化酰基吡啶为取代哌啶化合物盐酸盐的方法[P]. CN: 1995017A, 2006: 1-17.
[18] Chuan-Qing Kang, Yan-Qin Cheng, Hai-Quan Guo, et al. The natural alkaloid isoanabasine: synthesis from 2,3-bipyridine, efficient resolution with BINOL, and assignment of absolute configuration by Mosher’s method[J]. Tetrahedron: Asymmetry, 2005, 16(12): 2141–2147.
[19] Wang Wen-Bo, Lu Sheng-Mei, Yang Peng-Yu, et al. Highly Enantioselective Iridium-Catalyzed Hydrogenation of Heteroaromatic Compounds, Quinolines[J]. Journal of the American Chemical Society, 2003, 125(35): 10536-10537.
[20] Lu Sheng-Mei, Wang You-Qing, Han Xiu-Wen, et al. Asymmetric hydrogenation of quinolines and isoquinolines activated by chloroformates[J]. Angewandte Chemie, International Edition,2006, 45(14): 2260-2263.
[21]史泰尔斯等.催化剂载体与负载催化剂[M].中国:中国石化出版社, 1989:9-12.
[22] P. Albers, R. Burmeister, K. Seibold. Investigations of palladium catalysts on different carbon supports[J]. J. Catal, 1999, 181(1): 145-154.
[23] A. E. Aksoylu, Freitas, M. M. A. Figueiredo, J. L. Bimetallic. Pt-Sn catalysts supported on activated carbon. I. The effects of support modification and impregnation strategy[J]. Applied Catalysis, A: General, 2000, 192(1): 29-42.
[24] R. M. Navarro, B. Pawelec, J. M. Trejo, et al. Hydrogenation of Aromatics on Sulfur-Resistant Pt Pd Bimetallic Catalysts[J]. Journal of Catalysis, 2000, 189(1): 184-194.
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