Citation: ZHANG Pei-Zhi, YE Mei-Jun, HU Wei-Lian, WU Jun. Kinetics of Acid-Catalyzed Smiles Rearrangement of 2,6-Dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine Derivatives[J]. Acta Physico-Chimica Sinica, ;2016, 32(2): 422-428. doi: 10.3866/PKU.WHXB201512082 shu

Kinetics of Acid-Catalyzed Smiles Rearrangement of 2,6-Dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine Derivatives

ZHANG Pei-Zhi ^1,2,, ,
YE Mei-Jun ³ ,
HU Wei-Lian ¹ ,
WU Jun ^4,,

1.
1 School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. China;
2.
2 Key Laboratory of Recycling and Eco-treatment of Waste Biomass of Zhejiang Province, Zhejiang University of Science and Technology, Hangzhou 310023, P. R. China;
3.
3 Hangzhou Tea Research Institute, China COOP, Hangzhou 310016, P. R. China;
4.
4 Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China

Corresponding author: ZHANG Pei-Zhi, WU Jun,
Received Date: 24 August 2015
Available Online: 7 December 2015
Fund Project: 国家自然科学基金(31471807) (31471807)公益性行业(农业)科研专项(201403030)资助 (农业)科研专项(201403030)

The kinetics of the acid-catalyzed Smiles rearrangement reactions of 2,6-dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine derivatives was investigated. The effects of initial concentrations of hydrochloric acid, solvent, temperature, and substituent on reaction rates were examined. The results show that the rates increase with an increase in the initial concentration of hydrochloric acid. The reactivity order is CH₃OH > C₂H₅OH > CH₃SOCH₃ > CH₃CN in a single solvent, but rates markedly increase in mixed CH₃OH/H₂O (1:1, V/V) and the apparent reaction rate constant (k_obs) is 5.27 times that of methanol. The rates for the derivatives are found to increase with an increase in temperature at 25-45 ℃, and no significant differences in activation energy (73.99-76.92 kJ·mol^-1), activation enthalpy (71.57-74.38 kJ·mol^-1), and Gibbs free energy (81.51-85.77 kJ·mol^-1) are observed between them, except that there is difference in activation entropy (-24.38 --47.11 J·K^-1·mol^-1). There is a good linear relationship between substituents and the apparent reaction rate constants, and it is speculated that electron-withdrawing groups in the benzene ring will increase the reaction rates. A relevant reaction mechanism is suggested.
- Kinetics,
- Reaction mechanism,
- 2,6-Dimethoxy-2-pyrimidinyloxy-N-arylbenzylamine derivatives,
- Smiles rearrangement,
- Acid-catalyzed reaction
1. [1]
  (1) Liu, S. H.; Hu, Y.; Qian, P. F.; Hu, Y.W.; Ao, G. Z.; Chen, S.H.; Zhang, S. L.; Zhang, Y. N. Tetrahedron Lett. 2015, 56 (17), 2211. doi: 10.1016/j.tetlet.2015.03.062
2. [2]
  (2) Nechepurenko, I. V.; Komarova, N. I.; Shernyukov, A. V.; Vasiliev, V. G.; Salakhutdinov, N. F. Tetrahedron Lett. 2014, 55(44), 6125. doi: 10.1016/j.tetlet.2014.09.059
3. [3]
  (3) Xiao, Y. X.; Zhang, Z. C.; Chen, Y. B.; Shao, X. S.; Li, Z.; Xu, X. Y. Tetrahedron 2015, 71 (12), 1863. doi: 10.1016/j.tet.2015.01.059
4. [4]
  (4) Kitching, M. O.; Hurst, T. E.; Snieckus, V. Angew. Chem. Int.Edit. 2012, 51 (12), 2925. doi: 10.1002/anie.201106786
5. [5]
  (5) Yu, J. Z.; Wang, Y. T.; Zhang, P. Z.; Wu, J. Synlett 2013, 24(11), 1448. doi: 10.1055/s-00000083
6. [6]
  (6) Yu, J. Z.; Zhang, P. Z.; Wu, J.; Shang, Z. C. Tetrahedron Lett.2013, 54 (24), 3167. doi: 10.1016/j.tetlet.2013.04.028
7. [7]
  (7) Takahashi, T.; Maki, Y. Chem. Pharm. Bull. 1958, 6 (4), 369.
8. [8]
  (8) Rodig, O. R.; Collier, R. E.; Schlatzer, R. K. J. Org. Chem.1964, 29 (9), 2652.
9. [9]
  (9) Sunamoto, J.; Kondo, H.; Yanase, F.; Okamoto, H. B. Chem.Soc. Jpn. 1980, 53 (5), 1361.
10. [10]
  (10) Lindberg, P.; Nordberg, P.; Alminger, T.; Brandstrom, A.; Wallmark, B. J. Med. Chem. 1986, 29 (8), 1327.
11. [11]
  (11) Terauchi, H.; Tanitame, A.; Tada, K.; Nakamura, K.; Seto, Y.; Nishikawa, Y. J. Med. Chem. 1997, 40 (3), 313.
12. [12]
  (12) Kuhler, T. C.; Swanson, M.; Christenson, B.; Klintenberg, A.C.; Lamm, B.; Fagerhag, J.; Gatti, R.; Olwegard-Halvarsson, M.; Shcherbuchin, V.; Elebring, T. J. Med. Chem. 2002, 45(19), 4282.
13. [13]
  (13) Potashman, M. H.; Duggan, M. E. J. Med. Chem. 2009, 52 (5), 1231.
14. [14]
  (14) Shin, J. M.; Cho, Y. M.; Sachs, G. J. Am. Chem. Soc. 2004, 126(25), 7800.
15. [15]
  (15) Wu, J.; Cheng, J.; Lu, L. J. Arg. Food Chem. 2006, 54 (16), 5954. doi: 10.1021/jf061063p
16. [16]
  (16) Wu, J.; Zhang, P. Z.; Lü , L.; Yu, Q. S.; Hu, X. R.; Gu, J. M.Chin. J. Struct. Chem. 2003, 22 (5), 613. [吴军, 张培志, 吕龙, 俞庆森, 胡秀荣, 顾建明. 结构化学, 2003, 22 (5), 613.]
17. [17]
  (17) Wang, H. Y.; Zhang, X.; Guo, Y. L.; Tang, Q. H.; Lu, L. J. Am.Soc. Mass Spectrom. 2006, 17 (2), 253.
18. [18]
  (18) Wang, H. Y.; Liao, Y. X.; Guo, Y. L.; Tang, Q. H.; Lu, L.Synlett 2005, 8, 1239.
19. [19]
  (19) Wu, H. F.; Zhang, P. Z.; Wu, J. J. Zhejiang Univ. -Sci. B 2010, 11 (2), 94.
20. [20]
  (20) Wei, Y. Y.; Li, J. Z. An Introduction to Chemical Reaction Mechanism; Science Press: Beijing, 2003; pp 37-77. [魏运洋, 李建著. 化学反应机理导论. 北京: 科学出版社, 2003: 37-77.]
21. [21]
  (21) Richardson, D. E.; Yao, H. R.; Frank, K. M. Bennett, D. A.J. Am. Chem. Soc. 2000, 122 (8), 1729.
22. [22]
  (22) Zou, J.W.; Shang, Z. C.; Yi, P. G.; Yu, Q. S.; Lin, R. S. Chin.J. Org. Chem. 2000, 20 (4), 537. [邹建卫, 商志才, 易平贵, 俞庆森, 林瑞森. 有机化学, 2000, 20 (4), 537.]
23. [23]
  (23) Peng, M. J.; Lu, G. B.; Chen, W. H.; Chen, L. P.; Lü , J. Y. Acta Phys. -Chim. Sin. 2013, 29, 2095. [彭敏君, 路贵斌, 陈网桦, 陈利平, 吕家育. 物理化学学报, 2013, 29, 2095.] doi: 10.3866/PKU.WHXB201307122
24. [24]
  (24) Casey, C. P.; Singer, S.W.; Powell, D. R.; Hayashi, R. K.; Kavana, M. J. Am. Chem. Soc. 2001, 123 (6), 1090.
25. [25]
  (25) Zhu, X. Q.; Cao, L.; Liu, Y.; Yang, Y.; Lu, J. Y.; Wang, J. S.; Cheng, J. P. Chem. -Eur. J. 2003, 9 (16), 3937.
26. [26]
  (26) Hansch, C.; Leo, A.; Taft, R.W. Chem. Rev. 1991, 91 (2), 165.
27. [27]
  (27) Cao, C. T.; Wei, B. Y.; Cao, C. Z. Acta Phys. -Chim. Sin. 2015, 31, 204. [曹朝暾, 魏佰影, 曹晨忠. 物理化学学报, 2015, 31, 204.] doi: 10.3866/PKU.WHXB201412191
28. [28]
  (28) Hassan, R. M.; Alaraifi, A.; Fawzy, A.; Zaafarany, I. A.; Khairou, K. S.; Ikeda, Y.; Takagi, H. D. J. Mol. Catal. AChem.2010, 332, 138.
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