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
1. [1]
  Qiqi Li , Su Zhang , Yuting Jiang , Linna Zhu , Nannan Guo , Jing Zhang , Yutong Li , Tong Wei , Zhuangjun Fan . 前驱体机械压实制备高密度活性炭及其致密电容储能性能. Acta Physico-Chimica Sinica, 2025, 41(3): 2406009-. doi: 10.3866/PKU.WHXB202406009
2. [2]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
3. [3]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
4. [4]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
5. [5]
  Chengpeng Liu , Yinxia Fu . Design and Practice of Ideological and Political Education for the Public Elective Course “Life Chemistry Experiment” in Universities. University Chemistry, 2024, 39(10): 242-248. doi: 10.12461/PKU.DXHX202404064
6. [6]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
7. [7]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
8. [8]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
9. [9]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
10. [10]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
11. [11]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
12. [12]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
13. [13]
  Tao Cao , Fang Fang , Nianguang Li , Yinan Zhang , Qichen Zhan . Green Synthesis of p-Hydroxybenzonitrile Catalyzed by Spinach Extracts under Red-Light Irradiation: Research and Exploration of Innovative Experiments for Pharmacy Undergraduates. University Chemistry, 2024, 39(5): 63-69. doi: 10.3866/PKU.DXHX202309098
14. [14]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
15. [15]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
16. [16]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
17. [17]
  Ling Liu , Haibin Wang , Genrong Qiang . Curriculum Ideological and Political Design for the Comprehensive Preparation Experiment of Ethyl Benzoate Synthesized from Benzyl Alcohol. University Chemistry, 2024, 39(2): 94-98. doi: 10.3866/PKU.DXHX202304080
18. [18]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
19. [19]
  Ruitong Zhang , Zhiqiang Zeng , Xiaoguang Zhang . Improvement of Ethyl Acetate Saponification Reaction and Iodine Clock Reaction Experiments. University Chemistry, 2024, 39(8): 197-203. doi: 10.3866/PKU.DXHX202312004
20. [20]
  Bingliang Li , Yuying Han , Dianyang Li , Dandan Liu , Wenbin Shang . One-Step Synthesis of Benorilate Guided by Green Chemistry Principles and in vivo Dynamic Evaluation. University Chemistry, 2024, 39(6): 342-349. doi: 10.3866/PKU.DXHX202311070

Get Citation

PDF

XML

Metrics

PDF Downloads(1282)
Abstract views(3051)
HTML views(11)

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