酯加氢反应中影响羧基活化的因素

引用本文: 郑小娟, 周娅芬, 付海燕, 陈华, 李贤均, 李瑞祥. 酯加氢反应中影响羧基活化的因素[J]. 物理化学学报, 2010, 26(10): 2699-2704. doi: 10.3866/PKU.WHXB20100920 shu

Citation: ZHENG Xiao-Juan, ZHOU Ya-Fen, FU Hai-Yan, CHEN Hua, LI Xian-Jun, LI Rui-Xiang. Activation Factors for the Carboxyl Group in the Hydrogenation of Carboxylic Esters[J]. Acta Physico-Chimica Sinica, 2010, 26(10): 2699-2704. doi: 10.3866/PKU.WHXB20100920 shu

酯加氢反应中影响羧基活化的因素

基金项目:
国家自然科学基金(21072138)资助项目 (21072138)

摘要:

通过浸渍法制备4%Ru-9%La/γ-Al₂O₃ 催化剂, 采用X 射线衍射(XRD),X 射线光电子能谱(XPS) 和透射电子显微镜(TEM) 对其结构进行表征. 将该催化剂用于丙酸甲酯的加氢反应, 分别考察了溶剂、无机盐添加剂、底物空间因素及电子因素对酯加氢反应的影响. 发现以水为溶剂以及添加Co(NO₃)₂ 对丙酸甲酯加氢都显示出明显的促进作用, 底物的转化率及丙醇的选择性随之增加. 这是由于水及适量Co²⁺的引入能极化底物分子的C=O 键, 有利于活化氢对羧基碳原子的进攻, 改善催化剂的性能. 此外, 底物分子中吸电子基团能提高羧基碳原子的正电性, 也有利于加氢反应的进行; 而增大底物分子空间位阻, 不利于底物在催化剂上的吸附, 催化反应速率下降.

关键词:

催化加氢
/ 丙酸甲酯
/ 活化
/ 钌
/ 镧

English

Activation Factors for the Carboxyl Group in the Hydrogenation of Carboxylic Esters

1.
Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University,Chengdu 610064, P. R. China
Received Date: 29 April 2010
Available Online: 27 September 2010
Fund Project:
国家自然科学基金(21072138)资助项目

Abstract:

We prepared a 4%Ru-9%La/γ-Al₂O₃ catalyst by impregnation method and characterized it using X-ray diffraction(XRD) ,X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The catalyst was used for the hydrogenation of methyl propionate. The effects of solvent, inorganic salt additive, steric as well as electronic factors of the substrate on the hydrogenation of a carboxylic ester were investigated. We found that both water and the Co(NO₃)₂ additive obviously improved the hydrogenation of methyl propionate, the conversion of the substrate and the selectivity for propanol. The promotional effects of water and Co²⁺are attributed to polarization of the C=O bond in the carboxyl group of the substrate molecule by the formation of a hydrogen bond between water and the carboxylic group and the coordination of Co²⁺to the carboxylic group. This is favorable for an attack on the carbon atom of the carboxyl group by the activated hydrogen. Similarly, the electron -withdrawing group in the substrate molecule also caused the high positive charge of carbon in the carboxyl group. The highly positive charged carbon is beneficial for the hydrogenation reaction. In addition, an increase in the steric hindrance of the substrate molecules was not favorable for the adsorption of the substrate on the catalyst and, therefore, the reaction rate decreased.

Key words:

1. [1]
  
  1. McAlees, A. J. J. Chem. Soc. C, 1969: 2425
  1. McAlees, A. J. J. Chem. Soc. C, 1969: 2425
2. [2]
  2. Rieke, R. D.; Thakur, D. S.; Roberts, B. D.; White, G. T. J. Am. Oil Chem. Soc., 1997, 74(4): 3332. Rieke, R. D.; Thakur, D. S.; Roberts, B. D.; White, G. T. J. Am. Oil Chem. Soc., 1997, 74(4): 333
3. [3]
  3. Zhu, J. F. Preparation and characterization of middle-pressure hydrogenation catalyst for fatty acid methyl esters[D]. Qingdao: China University of Petroleum(East China), 2007 [朱建锋.脂肪酸甲酯中压加氢催化剂制备与表征[D]. 青岛: 中国石油大学 (华东), 2007]3. Zhu, J. F. Preparation and characterization of middle-pressure hydrogenation catalyst for fatty acid methyl esters[D]. Qingdao: China University of Petroleum(East China), 2007 [朱建锋.脂肪酸甲酯中压加氢催化剂制备与表征[D]. 青岛: 中国石油大学 (华东), 2007]
4. [4]
  4. Luo, G.; Yan, S. R.; Qiao, M. H.; Zhang, J. H.; Fan, K. N. Appl. Catal. A: Gen., 2004, 275: 954. Luo, G.; Yan, S. R.; Qiao, M. H.; Zhang, J. H.; Fan, K. N. Appl. Catal. A: Gen., 2004, 275: 95
5. [5]
  5. Bournonville, J. P.; Mabilon, G.; Candy, J. P.; Basset, J. M. J. Mol. Catal., 1991, 67: 2835. Bournonville, J. P.; Mabilon, G.; Candy, J. P.; Basset, J. M. J. Mol. Catal., 1991, 67: 283
6. [6]
  6. Corradini, S. A. S.; Lenzi, G. G.; Lenzi, M. K.; Soares, C. M. F.; Santos, O. A. A. Journal of Non-Crystalline Solids, 2008, 354: 48656. Corradini, S. A. S.; Lenzi, G. G.; Lenzi, M. K.; Soares, C. M. F.; Santos, O. A. A. Journal of Non-Crystalline Solids, 2008, 354: 4865
7. [7]
  7. Silva, A. M.; Morales, M. A.; Baggio-Saitovitch, E. M.; Jordão, E.; Fraga, M. A. Appl. Catal. A-Gen., 2009, 353: 1017. Silva, A. M.; Morales, M. A.; Baggio-Saitovitch, E. M.; Jordão, E.; Fraga, M. A. Appl. Catal. A-Gen., 2009, 353: 101
8. [8]
  8. Piccirilli, A.; Pouilloux, Y.; Pronier, S.; Barrault, J. Bull. Soc. Chim. France, 1995, 132: 11098. Piccirilli, A.; Pouilloux, Y.; Pronier, S.; Barrault, J. Bull. Soc. Chim. France, 1995, 132: 1109
9. [9]
  9. Pouilloux, Y.; Autin, F.; Barrault, J. Catal. Today, 2000, 63: 879. Pouilloux, Y.; Autin, F.; Barrault, J. Catal. Today, 2000, 63: 87
10. [10]
  10. Silva, A. M.; Santos, O. A. A.; Morales, M. A.; Baggio-Saitovitch, E. M.; Jordão, E.; Fraga, M. A. J. Mol .Catal. A, 2006, 253: 6210. Silva, A. M.; Santos, O. A. A.; Morales, M. A.; Baggio-Saitovitch, E. M.; Jordão, E.; Fraga, M. A. J. Mol .Catal. A, 2006, 253: 62
11. [11]
  11. Santos, S. M.; Silva, A. M.; Jordão, E.; Fraga, M. A. Catal. Today, 2005, 107-108: 25011. Santos, S. M.; Silva, A. M.; Jordão, E.; Fraga, M. A. Catal. Today, 2005, 107-108: 250
12. [12]
  12. Miyake, T.; Makino, T.; Taniguchi, S. I.; Watanuki, H.; Niki, T.; Shimizu, S.; Kojima, Y.; Sano, M. Appl. Catal. A-Gen., 2009, 364: 10812. Miyake, T.; Makino, T.; Taniguchi, S. I.; Watanuki, H.; Niki, T.; Shimizu, S.; Kojima, Y.; Sano, M. Appl. Catal. A-Gen., 2009, 364: 108
13. [13]
  13. Pouilloux, Y.; Autin, F.; Guimon, C.; Barrault, J. J. Catal., 1998, 176: 21513. Pouilloux, Y.; Autin, F.; Guimon, C.; Barrault, J. J. Catal., 1998, 176: 215
14. [14]
  14. Zhou, Y. F.; Fu, H. Y.; Zheng, X. J.; Li, R. X.; Chen, H.; Li, X. J. Catal. Commun., 2009, 11: 13714. Zhou, Y. F.; Fu, H. Y.; Zheng, X. J.; Li, R. X.; Chen, H.; Li, X. J. Catal. Commun., 2009, 11: 137
15. [15]
  15. Hu, S. C.; Chen, Y. W. J. Chem. Technol. Biotechnol., 2001, 76: 95415. Hu, S. C.; Chen, Y. W. J. Chem. Technol. Biotechnol., 2001, 76: 954
16. [16]
  16. Okada, K.; Nagashima, T.; Kameshima, Y.; Yasumori, A.; Tsukada, T. J. Colloid Interface Sci., 2002, 253: 30816. Okada, K.; Nagashima, T.; Kameshima, Y.; Yasumori, A.; Tsukada, T. J. Colloid Interface Sci., 2002, 253: 308
17. [17]
  17. Chen, X. Y.; Lee, S. W. Chem. Phys. Lett., 2007, 438: 27917. Chen, X. Y.; Lee, S. W. Chem. Phys. Lett., 2007, 438: 279
18. [18]
  18. Wang, J. Q.; Wang, Y. Z.; Xie, S. H.; Qiao, M. H.; Li, H. X.; Fan, K. N. Appl. Catal. A, 2004, 272: 2918. Wang, J. Q.; Wang, Y. Z.; Xie, S. H.; Qiao, M. H.; Li, H. X.; Fan, K. N. Appl. Catal. A, 2004, 272: 29
19. [19]
  19. Fleisch, T. H.; Hicks, R. F.; Bell, A. T. J. Catal., 1984, 87: 39819. Fleisch, T. H.; Hicks, R. F.; Bell, A. T. J. Catal., 1984, 87: 398
20. [20]
  20. Struijk, J.; Scholten, J. J. F. Appl. Catal. A, 1992, 82: 27720. Struijk, J.; Scholten, J. J. F. Appl. Catal. A, 1992, 82: 277
21. [21]
  21. Wehner, P. S.; Gustafson, B. L. J. Catal., 1992, 135: 42021. Wehner, P. S.; Gustafson, B. L. J. Catal., 1992, 135: 420
22. [22]
  22. Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem. Rev., 2004, 248: 220122. Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem. Rev., 2004, 248: 2201
23. [23]
  23. Nomura, K.; Ogura, H.; Imanishi, Y. J. Mol. Catal. A, 2001, 166: 34523. Nomura, K.; Ogura, H.; Imanishi, Y. J. Mol. Catal. A, 2001, 166: 345
24. [24]
  24. Zuo, B. J.;Wang, Y.;Wang, Q. L.; Zhang, J. L.; Wu, N. Z.; Peng, L. D. J. Catal., 2004, 222: 49324. Zuo, B. J.;Wang, Y.;Wang, Q. L.; Zhang, J. L.; Wu, N. Z.; Peng, L. D. J. Catal., 2004, 222: 493
25. [25]
  25. Xu, Q.; Liu, X. M.; Chen, J. R.; Li, R. X.; Li, X. J. J. Mol. Catal. A- Chem., 2006, 260: 299
  25. Xu, Q.; Liu, X. M.; Chen, J. R.; Li, R. X.; Li, X. J. J. Mol. Catal. A- Chem., 2006, 260: 299

扫一扫看文章

计量

PDF下载量: 1282
文章访问数: 3593
HTML全文浏览量: 47

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

酯加氢反应中影响羧基活化的因素

English

Activation Factors for the Carboxyl Group in the Hydrogenation of Carboxylic Esters

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

酯加氢反应中影响羧基活化的因素

English

Activation Factors for the Carboxyl Group in the Hydrogenation of Carboxylic Esters

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs