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

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 (21072138)

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.
- Catalytic hydrogenation,
- Methyl propionate,
- Activation,
- Ruthenium,
- Lanthanum
1. [1]
  
  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): 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]
4. [4]
  4. 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: 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: 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: 101
8. [8]
  8. 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: 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: 62
11. [11]
  11. 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: 108
13. [13]
  13. 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: 137
15. [15]
  15. 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: 308
17. [17]
  17. 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: 29
19. [19]
  19. 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: 277
21. [21]
  21. 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: 2201
23. [23]
  23. 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: 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
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