Citation: Shen Jingru, Li Lihong, Wang Xiaogang, Zhang Jia'nan, Jiang Zhenglin. Green Synthesis of 2, 2'-Bibenzazole and Its Polymers by Using Hexachloroacetone as C2 Synthon[J]. Chinese Journal of Organic Chemistry, ;2020, 40(12): 4322-4327. doi: 10.6023/cjoc202005059 shu

Green Synthesis of 2, 2'-Bibenzazole and Its Polymers by Using Hexachloroacetone as C2 Synthon

College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 200335

Corresponding author: Li Lihong, msriac@163.com
Received Date: 22 May 2020
Revised Date: 23 July 2020
Available Online: 18 August 2020

Figures(5)

A novel cyclization reaction by using hexachloroacetone as C2 synthon has been studied. The optimal condition was obtained by synthesis of bibenzothiazole in the presence hexachloroacetone in water. Experimental results showed that the nucleophilicity of substrates played a key role in the cyclization reaction, and catalytical amount of oxygen in reactions was also vital to trigger ring fusion in the formation of target compounds. Accordingly, the mechanism of cyclization reaction was proposed:the thiazole ring is formed in the first place by a nucleophillic attack of 2-aminobenzenethiol, followed by CCl₃ cleavage from hexachloroacetone. Then the second 2-aminobenzenethiol launches another nucleophilic attack, and three chloride ions leave to form the second thiazole ring. The method was applied to the substrates of 2, 5-diaminobenzene-1, 4-dithiol and benzene-1, 2, 4, 5-tetraamine, respectively and two polymers of polyphenylene dithiazole and polyphenylene diimidazole were successfully prepared. The experimental conditions were mild, the yield was high and the application value was high.
- hexachloroacetone,
- bibenzothiazole,
- bibenzimidazole,
- polyphenylene dithiazole,
- polyphenylene diimidazole
1. [1]
  Maynard, G. D. e-EROS Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Ltd, 2001, Chapter Hexachloroacetone 1.
2. [2]
  Traboni, S.; Liccardo, F.; Bedini, E.; Giordano, M.; Iadonisi, A. Tetrahedron Lett. 2017, 58, 1762. doi: 10.1016/j.tetlet.2017.03.068
3. [3]
  Marcos, C. R.; Carlos A. M.; Evandro L. D.; Cesar Z. Liebigs Ann. 1997, 925.
4. [4]
  Sheikhi, E.; Adib, M.; Akherati Karajabad, M.; Rezaei, N. ChemistrySelect 2019, 4, 13455. doi: 10.1002/slct.201903790
5. [5]
  (a) Omaka, N. O.; Ekennia, A. C.; Njoku, N. N.; Onwudiwe, D. C. Appl. Organomet. Chem. 2018, 32.
  (b) Richardson, C.; Richard, K. F. B.; Steel, P. J. Aust. J. Chem. 2008, 61, 183.
6. [6]
  Hamdi, A. E.; Helmut, G. A. Chin. J. Org. Chem. 2017, 37, 1824(in Chinese).
7. [7]
  Dar, A. A.; Shadab, M.; Khan, S.; Ali, N.; Khan, A. T. J. Org. Chem. 2016, 81, 3149. doi: 10.1021/acs.joc.6b00113
8. [8]
  (a) Osaheni, J. A.; Jenekhe, S. A. Macromolecules 1993, 26, 4726.
  (b) Conboy, G.; Taylor, R. G. D.; Findlay, N. J.; Kanibolotsky, A. L.; Inigo, A. R.; Ghosh, S. S.; Ebenhoch, B.; Krishnan Jagadamma, L.; Thalluri, G. K. V. V.; Sajjad, M. T.; Samuel, I. D. W.; Skabara, P. J. Mater. Chem. C 2017, 5, 11927.
  (c) Martin, S. J.; Bradley, D. D. C.; Osaheni, J. A.; Jenekhe, S. A. Mol. Cryst. Liq. Cryst. 2006, 256, 583.
9. [9]
  Hattori, T.; Akita, H.; Kakimoto, M.; Imai, Y. J. Polym. Sci. 1992, 30, 197.
10. [10]
  (a) Omaka, O. N.; Ekennia, A. C.; Njoku, N. N.; Onwudiwe, D. C. Appl. Organomet. Chem. 2018, 32.
  (b) Dar, A. A.; Shadab; Khan, S.; Ali, N.; Khan, A. T. J. Org. Chem. 2016, 81, 3149.
11. [11]
  Zhang, C.; Xu, J.; Zhao, X. Y.; Kang, C. M. J. Chem. Res. 2017, 9, 537.
12. [12]
  Addison, A. W.; Rao, T. N.; Wahlgren, C. G. J. Heterocycl. Chem. 1983, 20, 1481.
13. [13]
  (a) Huang, Q.; Qin, X.; Li, B.; Lan, J.; Guo, Q.; You, J. Chem. Commun. 2014, 50, 13739.
  (b) Elagab, H. A.; Alt, H. G. Turk. J. Chem.2016, 40, 667.
14. [14]
  (a) Preston, P. N. Chem. Rev.1974, 74, 279.
  (b) Holan, G.; Samuel, E. L.; Ennis, B. C.; Hinde, R. W. J. Chem. Soc., Perkin. 1 1967, 20.
  (c) Rezende, M. C.; Dall'Oglio, E. L.; Zucco, C. Synth. Commun. 2001, 31, 607.
15. [15]
  (a) Panetta, C. A.; Casanova, T. G. J. Org. Chem. 1970, 35, 2423.
  (b) Zucco, C.; Lima, C. F.; Rezende, M. C.; Vianna, J. F.; Nome, F. J. Org. Chem. 1987, 52, 5356.
  (c) Rezende, M. C.; Dall'Oglio, E. L.; Zucco, C. Tetrahedron Lett. 1996, 37, 5265.
16. [16]
  Addison, A. W.; Rao, T. N.; Wahlgren, C. G. J. Heterocycl. Chem. 1983, 20, 1481.
17. [17]
  Samanta, S.; Das, S.; Biswas, P. J. Org. Chem. 2013, 78, 11184. doi: 10.1021/jo401445j
18. [18]
  (a) Farahi, M.; Karami, B.; Azari, M. C. R. Chim. 2013, 16, 1029.
  (b) Mazlumi, M.; Shirini, F.; Goli-Jolodar, O.; Seddighi, M. New J. Chem. 2018, 42, 5742.
19. [19]
  (a) Freedlander, R. S.; Bryson, T. A.; Dunlap, R. B.; Schulman, E. M.; Lewis, C. A. J. Org. Chem. 1981, 46, 3519.
  (b) Tauer, E.; Grellmann, K. H. J. Am. Chem. Soc.1981, 4252.
20. [20]
  Spengler, J.; Böttcher, C.; Albericio, F.; Burger, K. Chem. Rev. 2006, 106, 4728. doi: 10.1021/cr0509962
21. [21]
  Conboy, G.; Taylor, R. G. D.; Findlay, N. J.; Kanibolotsky, A. L.; Inigo, A. R.; Ghosh, S. S.; Ebenhoch, B.; Krishnan Jagadamma, L.; Thalluri, G. K. V. V.; Sajjad, M. T.; Samuel, I. D. W.; Skabara, P. J. J. Mater. Chem. C 2017, 5, 11927. doi: 10.1039/C7TC03959J
22. [22]
  Boyer, J. I.; Buriks, R. S. Org. Synth. 1960, 40, 96. doi: 10.15227/orgsyn.040.0096
23. [23]
  Rai, C.; Braunwarth, J. B. J. Org. Chem. 2002, 26, 3434.
24. [24]
  Rezende, M. C.; Dall'Oglio, E. L.; Zucco, C. Tetrahedron Lett. 1996, 37, 5265. doi: 10.1016/0040-4039(96)01115-X
25. [25]
  Omaka, O. N.; Ekennia, A. C.; Njoku, N. N.; Onwudiwe, D. C. Appl. Organomet. Chem. 2018, 32, 2.
26. [26]
  Rezende, M. C.; Marques, C. A.; Dall'Oglio, E. L.; Zucco, C. Liebigs Ann. 1997, 928.
27. [27]
  John, A.; Osaheni; Samson, A.; Jenekhe Chem. Mater. 1992, 4, 1286.
28. [28]
  Osaheni, J. A.; Jenekhe, S. A. Macromolecules 1995, 28, 1173.
29. [29]
  He, D.; Wu, Y.; Xu, B.-Q. Eur. Polym. J. 2007, 43, 3705.
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