Acta Phys. -Chim. Sin. ›› 2018, Vol. 34 ›› Issue (8): 952-958.doi: 10.3866/PKU.WHXB201803081

Special Issue: 绿色化学

• ARTICLE • Previous Articles    

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

Bihua CHEN1,H. M. ELAGEED Elnazeer1,2,Yongya ZHANG1,Guohua GAO1,*()   

  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
  • Received:2018-01-29 Published:2018-04-03
  • Contact: Guohua GAO E-mail:ghgao@chem.ecnu.edu.cn
  • Supported by:
    The project was supported by the National Key Research and Development Program of China(2017YFA0403102);National Natural Science Foundation of China(21773068);National Natural Science Foundation of China(21573072);Shanghai Leading Academic Discipline Project, China(B409)

Abstract:

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.

Key words: Ionic liquids, Homogeneous catalysis, Reaction mechanism, Condensation, 3-Arylthiazolidine-2-thiones

MSC2000: 

  • O643