Citation: LI Jia, XU Wen-Li, HU Jing, LING Min, YAO Jian-Hua. Hydrolysis Reaction Mechanismof 2, 4-Dichlorophenoxy Acetic Acid Metabolism[J]. Acta Physico-Chimica Sinica, ;2013, 29(09): 1923-1930. doi: 10.3866/PKU.WHXB201306281 shu

Hydrolysis Reaction Mechanismof 2, 4-Dichlorophenoxy Acetic Acid Metabolism

1.
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China

Received Date: 6 February 2013
Available Online: 28 June 2013
Fund Project: 国家自然科学基金项目(21072216) (21072216)支撑项目(2011BAE06B05) (2011BAE06B05)国家重点基础研究发展规划项目(973)(2010CB126103)资助 (973)(2010CB126103)

2,4-Dichlorophenoxy acetic acid (2,4-D) is a herbicide and plant growth regulator that is widely applied inagriculture.Many chemical reactions takeplace inthemetabolismof 2,4-D. Herein, the hydrolysis reaction mechanismin 2,4-D metabolismwill be presented. In this study, a density functional theory approach, B3LYP, was employed toinvestigatethehydrolysis reaction mechanismalong three different paths. The computed results indicate that: (Ⅰ) there are two models of the hydrolysis reaction of 2,4-D. The dissociation mechanismof C(1)―O and C―Cl involve hydrogen transfer and Cl substitution, respectively. (Ⅱ) The energy barrier of C―Cl dissociation was lower and the dissociation showed advantageous dynamics. Two of the reaction paths that initiate the dissociation of C―Cl were primary reactions. The dissociation of C(1)―O was the last step in the primary reactions and had a higher energy barrier. In metabolism, the different intermediates have different concentrations, and this impacts on the reaction rate. (Ⅲ) In addition, it was necessary to consider the solvent effect to investigate the hydrolysis reaction. To characterize the solvent effect, the conductor-like polarizable continuum model (CPCM) was used to simulate the hydrolysis reaction with respect to the bond length and energy barrier.
- 2,4-Dichlorophenoxy aceitc acid,
- Density functional theory,
- Reaction mechanism,
- Potential energy surface,
- Hydrolysis,
- Solvent effect
1. [1]
  
  (1) Zeljezic, D.; Garaj-Vrhovac, V. Toxicology 2004, 200 (1), 39.doi: 10.1016/j.tox.2004.03.002
2. [2]
  (2) Lerch, T. Z.; Dignac, M. F.; Barriuso, E.; Bardoux, G.; Mariotti,A. J. Microbiol. Meth. 2007, 71, 162. doi: 10.1016/j.mimet.2007.08.003
3. [3]
  (3) e-Pesticide Manual V4.2, version 4.2, copyright BCPC, 2008-2009, Publisher BCPC.
4. [4]
  (4) Colborn, E.; VomSaal, F. S.; Soto, A. M. Environmental Impact Assessment Review 1993, 14, 469.
5. [5]
  (5) Zeep, R. G.; Wolfe, N. L.; rdon, J. A.; Baughman, G. L.Environ. Sci. Technol. 1975, 9, 1144. doi: 10.1021/es60111a001
6. [6]
  (6) Hoover, D. G.; Bor nov, G. E.; Jones, S. H. Appl. Environ. Microb. 1986, 51, 226.
7. [7]
  (7) Luna, A. J.; Chiavone-Filho, O.; Machulek, A.; de Moraes, J. E.F.; Nascimento, C. A. O. J. Environ. Manage. 2012, 111, 10.doi: 10.1016/j.jenvman.2012.06.014
8. [8]
  (8) Cabrera, M. I.; Martin, C. A.; Alfano, O. M. Water Sci. Technol.1997, 35 (4), 31.
9. [9]
  (9) Lee, Y.; Lee, C.; Yoon, J. Chemosphere 2003, 51, 963. doi: 10.1016/S0045-6535(03)00043-2
10. [10]
  (10) Wang, Q.; Lemley, A. T. Environ. Sci. Technol. 2001, 35, 4509.doi: 10.1021/es0109693
11. [11]
  (11) Rivera-Utrilla, J.; Sánchez-Polo, M.; Abdel daiem, M. M.;Ocampo-Pérez, R. Appl. Catal. B-Environ. 2012, 126, 100. doi: 10.1016/j.apcatb.2012.07.015
12. [12]
  (12) Seck, E. I.; Dona-Rodríguez, J. M.; Fernández-Rodriguez, C.; nzález-Díaz, O. M.; Arana, J.; Pérez-Pena, J. Appl. Catal. BEnviron.2012, 125, 28. doi: 10.1016/j.apcatb.2012.05.028
13. [13]
  (13) Laurent, F.; Debrauwer, L.; Rathahao, E.; Scalla, R. J. Agric. Food Chem. 2000, 48 (11), 5307. doi: 10.1021/jf990672c
14. [14]
  (14) Niedrée, B.; Vereecken, H.; Burauel, P. J. Environ. Radioactiv.2013, 115, 168. doi: 10.1016/j.jenvrad.2012.08.008
15. [15]
  (15) Fontmorin, J. M.; Huguet, S.; Fourcade, F.; Geneste, F.; Floner,D.; Amrane, A. Chem. Eng. J. 2012, 195, 208.
16. [16]
  (16) Tiedje, J. M.; Duxbury, J. M.; Alexander, M.; Dawson, J. E.J. Agric. Food Chem. 1969, 17 (5), 1021. doi: 10.1021/jf60165a037
17. [17]
  (17) Hagin, R. D.; Linscott, D. L.; Dawson, J. E. J. Agric. Food Chem. 1970, 18 (5), 848. doi: 10.1021/jf60171a030
18. [18]
  (18) Hamilton, R. H.; Hurter, J.; Hall, J. K.; Erce vich, C. D.J. Agric. Food Chem. 1971, 19 (3), 480. doi: 10.1021/jf60175a031
19. [19]
  (19) Crosby, D. G.; Tutass, H. O. J. Agric. Food Chem. 1966, 14 (6),596. doi: 10.1021/jf60148a012
20. [20]
  (20) Linscott, D. L.; Hagin, R. D.; Dawson, J. E. J. Agric. Food Chem. 1968, 16 (5), 844. doi: 10.1021/jf60159a035
21. [21]
  (21) Feung, C. S.; Hamilton, R. H.; Mumma, R. O. J. Agric. Food Chem. 1973, 21 (4), 637. doi: 10.1021/jf60188a058
22. [22]
  (22) Roberts, T. R. Metabolic Pathways of Agrochemicals; TheRoyal Society of Chemistry: Cambridge, UK, 1998; pp 66-74.
23. [23]
  (23) Barone, V.; Cossi, M. J. Phys. Chem. 1998, 102 (11), 1995. doi: 10.1021/jp9716997
24. [24]
  (24) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 09,Revision A.02; Gaussian Inc.: Pittsburgh, PA, 2009.
25. [25]
  (25) Perdew, J. P. Phys. Rev. B 1986, 33, 8800. doi: 10.1103/PhysRevB.33.8800
26. [26]
  (26) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
27. [27]
  (27) Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971,54, 724. doi: 10.1063/1.1674902
28. [28]
  (28) Deng, L.; Ziegler, T.; Fan, L. J. J. Chem. Phys. 1993, 99, 3823.doi: 10.1063/1.466129
29. [29]
  (29) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88,899. doi: 10.1021/cr00088a005
30. [30]
  (30) Jia, X. J.; Pan, X. M.; Wang, L. W.; Liu, Y.; Sun, H.; Su, Z. M.;Wang, R. S. Chem. J. Chin. Univ. 2008, 29, 1224. [贾秀娟,潘秀梅, 王莉伟,刘颖,孙昊,苏忠民, 王荣顺.高等学校化学学报, 2008, 29, 1124.]
31. [31]
  (31) Yi, G. Q.; Zeng, Y.; Xia, X. F. Chem. Phys. 2008, 345 (1), 73.doi: 10.1016/j.chemphys.2008.01.036
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Xiaolong Zhang , Mingshan Jin , Shaoli Liu , Bingfei Yan , Yun Li . Constructing High-Precision Potential Energy Surfaces Based on Physical Models: A Comprehensive Computational Chemistry Experiment. University Chemistry, 2025, 40(10): 257-262. doi: 10.12461/PKU.DXHX202411049
3. [3]
  Jia Zhou . Constructing Potential Energy Surface of Water Molecule by Quantum Chemistry and Machine Learning: Introduction to a Comprehensive Computational Chemistry Experiment. University Chemistry, 2024, 39(3): 351-358. doi: 10.3866/PKU.DXHX202309060
4. [4]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
5. [5]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
6. [6]
  Anqi LI , Wenjing YANG , Xueming LI , Yanfong REN . Performance and mechanism of a foam Ti/FeCo-Fe₂O₃-CoFe₂O₄/SnO₂-Sb anode for synergistic activation of peroxymonosulfate toward degradation of organic pollutants. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 944-958. doi: 10.11862/CJIC.20250323
7. [7]
  Guowen Xing , Guangjian Liu , Le Chang . Five Types of Reactions of Carbonyl Oxonium Intermediates in University Organic Chemistry Teaching. University Chemistry, 2025, 40(4): 282-290. doi: 10.12461/PKU.DXHX202407058
8. [8]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
9. [9]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
10. [10]
  Yuai Duan , Xuanyu Gan , Yao Fu , Yingjie Cao , Hongliang Han , Zhanfang Ma . Application and Innovative Design of Digital Technology in the Preparation Experiment of Cis(Trans)-Diglycine Copper Complexes. University Chemistry, 2026, 41(1): 373-381. doi: 10.12461/PKU.DXHX202504048
11. [11]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
12. [12]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
13. [13]
  Hao Wu , Fengqi Li , Xinwei Shi , Haifeng Bian , Qing Zhou , Shunshun Jia , Yujie Ma , Jian Gu , Jingzi Zhang , Shuijian He , Xiangkang Meng . Machine-learning guides discovery of multi-principal element alloys as electrocatalyst for hydrogen evolution reaction. Acta Physico-Chimica Sinica, 2026, 42(8): 100227-0. doi: 10.1016/j.actphy.2025.100227
14. [14]
  Shuangshuang Mao , Juhua Luo , Bingjie Han , Jiahuan Shi , Yujia Gu . Covalent organic framework-derived Fe₃C/NC/TiO₂ heterostructures for high-performance electromagnetic wave absorption. Acta Physico-Chimica Sinica, 2026, 42(7): 100290-. doi: 10.1016/j.actphy.2026.100290
15. [15]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
16. [16]
  Lijun Yang . Thoughts and Practices on Enhancing Students’ Comprehension through Visualized Instruction of Structural Chemistry. University Chemistry, 2025, 40(10): 295-302. doi: 10.12461/PKU.DXHX202411048
17. [17]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
18. [18]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
19. [19]
  Zhi Chai , Huashan Huang , Xukai Shi , Yujing Lan , Zhentao Yuan , Hong Yan . Wittig反应的立体选择性. University Chemistry, 2025, 40(8): 192-201. doi: 10.12461/PKU.DXHX202410046
20. [20]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045

Get Citation

PDF

XML

Metrics

PDF Downloads(789)
Abstract views(2013)
HTML views(31)

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