Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

Shen, Yu‐Mei; Shi, Min

doi:10.1002/aoc.497

Cited by 5 publications

(2 citation statements)

References 30 publications

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“…CS 2 is a sulfur analogue of CO 2 which can also be considered as an attractive C1 building block to synthesize sulfurcontaining functional molecules. There are only a few examples about cycloaddition of CS 2 with aziridines [20,55], epoxides [15,[56][57][58] and propargyl amines [32,59]. In this context, we further extended this catalytic system to the reaction involving CS 2 .…”

Section: Methodsmentioning

confidence: 99%

Environmentally benign chemical fixation of CO2 catalyzed by the functionalized ion-exchange resins

Liu

Peng

et al. 2010

Sci. China Chem.

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Section: Methodsmentioning

confidence: 99%

Environmentally benign chemical fixation of CO2 catalyzed by the functionalized ion-exchange resins

Liu

Peng

et al. 2010

Sci. China Chem.

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“…Besides, they also have been used as selective acylating agents 8 , chiral auxiliaries 9 , and ligands in coordination chemistry 10,11 . Therefore, many strategies have been developed for the synthesis of thiazolidine-2-thiones, including the cycloaddition of aziridines with carbon disulfide (CS2) 12,13 , the iodocyclization of allyl amines, CS2 and iodine 14 , the reaction of propargylamines with CS2 15,16 , and the reaction of 2-amino ethanol with trithiocarbonates 17 . These approaches have some disadvantages such as the use of toxic or expensive catalysts, hazardous materials, long reaction time, or high reaction temperature.…”

Section: Introductionmentioning

confidence: 99%

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

CHEN¹,

Elnazeer²,

ZHANG³

et al. 2018

Acta Physico-Chimica Sinica

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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-2thiones by direct condensation of 2-(arylamino) alcohols with carbon disulfide (CS2) catalyzed by the ionic liquid 1butyl-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 °C; 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. 1 H and 13 C 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.

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