Citation: CHEN Bihua, ELAGEED Elnazeer H. M., ZHANG Yongya, GAO Guohua. BmmimOAc-Catalyzed Direct Condensation of 2-(Arylamino) Alcohols to Synthesize 3-Arylthiazolidine-2-thiones[J]. Acta Physico-Chimica Sinica, ;2018, 34(8): 952-958. doi: 10.3866/PKU.WHXB201803081 shu

BmmimOAc-Catalyzed Direct Condensation of 2-(Arylamino) Alcohols to Synthesize 3-Arylthiazolidine-2-thiones

CHEN Bihua ^1,† ,
ELAGEED Elnazeer H. M. ^1,2,† ,
ZHANG Yongya ¹ ,
GAO Guohua ^1,,

1.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. China
2.
Department of Chemistry, Faculty of Education, University of Khartoum, Umdurman 406, Sudan

Corresponding author: GAO Guohua, ghgao@chem.ecnu.edu.cn

^†

Received Date: 29 January 2018
Revised Date: 5 March 2018
Accepted Date: 5 March 2018
Available Online: 8 August 2018
Fund Project: National Natural Science Foundation of China 21773068National Natural Science Foundation of China 21573072The project was supported by the National Key Research and Development Program of China (2017YFA0403102), National Natural Science Foundation of China (21773068, 21573072), and Shanghai Leading Academic Discipline Project, China (B409)The project was supported by the National Key Research and Development Program of China 2017YFA0403102Shanghai Leading Academic Discipline Project, China B409

Thiazolidine-2-thiones have attracted much attention because of their unique bioactivity and have been widely used in the fields of medicine and synthetic heterocyclic chemistry. In this work, a simple and convenient route for the synthesis of 3-arylthiazolidine-2-thiones by direct condensation of 2-(arylamino) alcohols with carbon disulfide (CS₂) catalyzed by the ionic liquid 1-butyl-2, 3-dimethylimidazolium acetate (BmmimOAc) has been developed. A series of ionic liquids were used as catalysts in the model reaction of 2-(phenylamino) ethanol with CS₂. The results showed that only the acetate ionic liquids have catalytic activity, perhaps owing to the basicity of the acetate anion. Among these acetate ionic liquids, BmmimOAc showed the highest catalytic activity and was selected as the best catalyst. The effects of reaction time, reaction temperature, amount of BmmimOAc, and CS₂ to 2-(phenylamino) ethanol molar ratio were investigated in detail. The following were found to be the optimal reaction conditions for direct condensation of 2-(phenylamino) ethanol with CS₂: reaction time, 6 h; reaction temperature, 130 ℃; 10% molar fraction of BmmimOAc; and CS₂ to 2-(phenylamino) ethanol molar ratio of 5 : 1. Under these optimized reaction conditions, the product 3-phenylthiazolidine-2-thione was obtained in 97% yield. The reaction scope was explored by investigating the reactions of various 2-(arylamino) alcohols with CS₂. The results showed that the 2-(arylamino) alcohols with electron-donating substituents, electron-withdrawing substituents, or high steric hindrance could be smoothly converted to the corresponding products in excellent isolated yields of 83%–95%. NMR characterizations and mass spectrum indicated that the acetate anion of BmmimOAc could react spontaneously with CS₂ to form the thioacetate anion (CH₃COS⁻). Ionic liquid 1-butyl-2, 3-dimethylimidazolium thioacetate (BmmimCOS) might be the actual catalyst in the reaction of 2-(arylamino) alcohols with CS₂. ¹H and ¹³C NMR spectroscopies were used to study the interactions between BmmimCOS and substrates 2-(phenylamino) ethanol and CS₂. The NMR spectra showed the hydrogen bonding interactions between BmmimCOS and 2-(phenylamino) ethanol. The CH₃COS⁻ anion of BmmimCOS could activate the 2-(phenylamino) ethanol in the catalytic system. Based on the characterization results, a possible reaction mechanism was proposed. Firstly, BmmimOAc reacted spontaneously with CS₂ to form BmmimCOS. Then, CH₃COS⁻ of BmmimCOS activated 2-(phenylamino) ethanol via hydrogen bonding. Subsequently, CS₂ reacted with the activated 2-(phenylamino) ethanol to form the intermediate. Finally, the intermediate was subjected to intramolecular cyclization to form the final product 3-phenylthiazolidine-2-thione.
- Ionic liquids,
- Homogeneous catalysis,
- Reaction mechanism,
- Condensation,
- 3-Arylthiazolidine-2-thiones
1. [1]
  Prabhakar Y. S., Solomon V. R., Gupta M. K., Katti S. B.. QSAR Studies on Thiazolidines: A Biologically Privileged Scaffold[J]. In QSAR and Molecular Modeling Studies in Heterocyclic Drugs Ⅱ; Gupta S. P...Ed.; Springer: Berlin, Germany, 2006:pp. 161-249.
2. [2]
  Chen, N.; Du, H.; Liu, W.; Wang, S.; Li, X.; Xu, J. Phosphorus Sulfur Silicon 2015, 190, 112. doi: 10.1080/10426507.2014.931399 doi: 10.1080/10426507.2014.931399
3. [3]
  Almeida, A. M.; Oliveira, B. A.; Castro, P. P.; Mendon a, C. C.; Furtado, R. A.; Diniz, H. N.; Silva, V. L.; Diniz, C. G.; Tavares, D. C.; Silva, H.; et al. Biometals 2017, 30, 841. doi: 10.1007/s10534-017-0046-6 doi: 10.1007/s10534-017-0046-6
4. [4]
  Li, R.; Ning, X.; Zhou, S.; Lin, Z.; Wu, X.; Chen, H.; Bai, X.; Wang, X.; Ge, Z.; Li, R.; et al. Eur. J. Med. Chem. 2018, 143, 48. doi: 10.1016/j.ejmech.2017.11.023 doi: 10.1016/j.ejmech.2017.11.023
5. [5]
  Corrêa, R. S.; Silva, M. M.; Graminha, A. E.; Meira, C. S.; Santos, J. A. F.; Moreira, D. R. M.; Soares, M. B. P.; Poelhsitz, G. V.; Castellano, E. E.; Bloch, C.; et al. J. Inorg. Biochem. 2016, 156, 153. doi: 10.1016/j.jinorgbio.2015.12.024 doi: 10.1016/j.jinorgbio.2015.12.024
6. [6]
  Makiabadi, B. J. Sulfur Chem. 2015, 36, 494. doi: 10.1080/17415993.2015.1062097 doi: 10.1080/17415993.2015.1062097
7. [7]
  Hirata, T.; Kogiso, H.; Morimoto, K.; Miyamoto, S.; Taue, H.; Sano, S.; Muguruma, N.; Ito, S.; Nagao, Y. Bioorg. Med. Chem. 1998, 6, 2179. doi: 10.1016/S0968-0896(98)00156-4 doi: 10.1016/S0968-0896(98)00156-4
8. [8]
  Yamada, S. Tetrahedron Lett. 1992, 33, 2171. doi: 10.1016/0040-4039(92)88169-6 doi: 10.1016/0040-4039(92)88169-6
9. [9]
  Nagao, Y.; Hagiwara, Y.; Kumagai, T.; Ochiai, M.; Inoue, T.; Hashimoto, K.; Fujita, E. J. Org. Chem. 1986, 51, 2391. doi: 10.1021/jo00362a047 doi: 10.1021/jo00362a047
10. [10]
  Lobana, T. S.; Rani, A.; Butt, Y. N.; Jasinski, J. P. J. Sulfur Chem. 2015, 36, 251. doi: 10.1080/17415993.2015.1023802 doi: 10.1080/17415993.2015.1023802
11. [11]
  Fabretti, A. C.; Ferrari, M.; Franchini, G. C.; Preti, C.; Tassi, L.; Tosi, G. Transit. Met. Chem. 1982, 7, 279. doi: 10.1007/BF00618715 doi: 10.1007/BF00618715
12. [12]
  Clapp, L. B.; Watjen, J. W. J. Am. Chem. Soc. 1953, 75, 1490. doi: 10.1021/ja01102a516 doi: 10.1021/ja01102a516
13. [13]
  Sudo, A.; Morioka, Y.; Koizumi, E.; Sanda, F.; Endo, T. Tetrahedron Lett. 2003, 44, 7889. doi: 10.1016/j.tetlet.2003.09.011 doi: 10.1016/j.tetlet.2003.09.011
14. [14]
  Ziyaei-Halimehjani, A.; Marjani, K.; Ashouri, A. Tetrahedron Lett. 2012, 53, 3490. doi: 10.1016/j.tetlet.2012.04.129 doi: 10.1016/j.tetlet.2012.04.129
15. [15]
  Shi, M.; Shen, Y. Heteroatom Chem. 2001, 12, 610. doi: 10.1002/hc.1092 doi: 10.1002/hc.1092
16. [16]
  Shen, Y.; Shi, M. Appl. Organometal. Chem. 2003, 17, 767. doi: 10.1002/aoc.497 doi: 10.1002/aoc.497
17. [17]
  Taguchi, T.; Kiyoshima, Y.; Komori, O.; Mori, M. Tetrahedron Lett. 1969, 10, 3631. doi: 10.1016/S0040-4039(01)88473-2 doi: 10.1016/S0040-4039(01)88473-2
18. [18]
  Delaunay, D; Toupet, L.; Corre, M. L. J. Org. Chem. 1995, 60, 6604. doi: 10.1021/jo00125a059 doi: 10.1021/jo00125a059
19. [19]
  Chen, N.; Jia, W.; Xu, J. X. Eur. J. Org. Chem. 2009, 5841. doi: 10.1002/ejoc.200900759 doi: 10.1002/ejoc.200900759
20. [20]
  Welton, T. Chem. Rev. 1999, 99, 2071. doi: 10.1021/cr980032t doi: 10.1021/cr980032t
21. [21]
  Hallett, J. P.; Welton, T. Chem. Rev. 2011, 111, 3508. doi: 10.1021/cr1003248 doi: 10.1021/cr1003248
22. [22]
  Zhang, P.; Wu, T.; Han, B. Adv. Mater. 2014, 26, 6810. doi: 10.1002/adma.201305448 doi: 10.1002/adma.201305448
23. [23]
  Zhang, Z.; Song, J.; Han, B. Chem. Rev. 2017, 117, 6834. doi: 10.1021/acs.chemrev.6b00457 doi: 10.1021/acs.chemrev.6b00457
24. [24]
  MacFarlane, D. R.; Pringle, J. M.; Johansson, K. M.; Forsyth, S. A.; Forsyth, M. Chem. Commun. 2006, 1905. doi: 10.1039/B516961P doi: 10.1039/B516961P
25. [25]
  Zhang, L.; Fu, X.; Gao, G. ChemCatChem 2011, 3, 1359. doi: 10.1002/cctc.201100016 doi: 10.1002/cctc.201100016
26. [26]
  Wang, B.; Elageed, E. H. M.; Zhang, D.; Yang, S.; Wu, S.; Zhang, G.; Gao, G. ChemCatChem 2014, 6, 278. doi: 10.1002/cctc.201300801 doi: 10.1002/cctc.201300801
27. [27]
  Wang, B.; Yang, S.; Min, L.; Gu, Y.; Zhang, Y.; Wu, X.; Zhang, L.; Elageed, E. H. M.; Wu, S.; Gao, G. Adv. Synth. Catal. 2014, 356, 3125. doi: 10.1002/adsc.201400026 doi: 10.1002/adsc.201400026
28. [28]
  Elageed, E. H. M.; Wang, B.; Zhang, Y.; Wu, S.; Gao, G. J. Mol. Catal. A: Chem. 2015, 408, 271. doi: 10.1016/j.molcata.2015.07.034 doi: 10.1016/j.molcata.2015.07.034
29. [29]
  Zhang, L.; Yang, S.; Gao, G. Chin. J. Catal. 2011, 32, 1875. doi: 10.3724/SP.J.1088.2011.10757 doi: 10.3724/SP.J.1088.2011.10757
30. [30]
  Elageed, E. H. M.; Chen, B.; Wang, B.; Zhang, Y.; Wu, S.; Liu, X.; Gao, G. Eur. J. Org. Chem. 2016, 3650. doi: 10.1002/ejoc.201600474 doi: 10.1002/ejoc.201600474
31. [31]
  Zhang, Y.; Wang, B.; Elageed, E. H. M.; Qin, L.; Ni, B.; Liu, X.; Gao, G. ACS Macro. Lett. 2016, 5, 435. doi: 10.1021/acsmacrolett.6b00178 doi: 10.1021/acsmacrolett.6b00178
32. [32]
  Zhang, Y.; Zhang, Y.; Chen, B.; Qin, L.; Gao, G. ChemistrySelect2017, 2, 9443. doi: 10.1002/slct.201702081 doi: 10.1002/slct.201702081
33. [33]
  Caba o, M. I.; Besnard, M.; Chavez, F. V.; Pinaud, N.; Sebastiao, P. J.; Coutinho, J. A. P.; Mascetti, J.; Danten, Y. Chem. Commun. 2013, 49, 11083. doi: 10.1039/c3cc46038j doi: 10.1039/c3cc46038j
34. [34]
  Caba o, M. I.; Besnard, M.; Chavez, F. V.; Pinaud, N.; Sebastiao, P. J.; Coutinho, J. A. P.; Danten, Y. J. Chem. Phys. 2014, 140, 244307. doi: 10.1063/1.4884820 doi: 10.1063/1.4884820
35. [35]
  Wang, B.; Qin, L.; Mu, T.; Xue, Z.; Gao, G. Chem. Rev. 2017, 117, 7113. doi: 10.1021/acs.chemrev.6b00594 doi: 10.1021/acs.chemrev.6b00594
36. [36]
  Chen, X.; Song, H.; Chen, P.; Wang, F.; Qian, Y.; Li, X. Acta Chim. Sin. 2012, 70, 770. doi: 10.6023/A1108223
37. [37]
  Ortiz, A.; Sansinenea, E. J. Sulfur Chem. 2007, 28, 109. doi: 10.1080/17415990601139699 doi: 10.1080/17415990601139699
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