Water-Promoted Green Synthesis of Heteroaryl Thioether

doi:10.6023/cjoc202211004

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (6): 2136-2142.DOI: 10.6023/cjoc202211004 Previous Articles Next Articles

水促进下杂芳基硫醚的绿色合成

马献涛^*(), 闫晓雨, 朱影影, 牛双林, 王喻璇, 袁超

信阳师范学院化学化工学院信阳市绿色催化和合成重点实验室信阳 464000

收稿日期:2022-11-02 修回日期:2023-01-02 发布日期:2023-01-11
基金资助:
国家自然科学基金(22101243); 信阳师范学院南湖学者青年计划; 河南省大学生创新创业计划训练计划(202210477010); 信阳师范学院大学生科研基金(2022-DXS-089)

Water-Promoted Green Synthesis of Heteroaryl Thioether

Xiantao Ma^*(), Xiaoyu Yan, Yingying Zhu, Shuanglin Niu, Yuxuan Wang, Chao Yuan

Green Catalysis & Synthesis Key Laboratory of Xinyang City, College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000

Received:2022-11-02 Revised:2023-01-02 Published:2023-01-11
Contact: * E-mail: xiantaoma@126.com
Supported by:
National Natural Science Foundation of China(22101243); Nanhu Scholars Program for Young Scholars of Xinyang Normal University; Training Program of Innovation and Entrepreneurship Plan for College Students in Henan Province(202210477010); Research and Innovation Projects for College Students of Xinyang Normal University(2022-DXS-089)

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Abstract

Heteroaryl thioethers are a class of important bioactive molecules, which exhibit good antibacterial, anti- inflammatory and anticancer activities. In this paper, a new, base-free and green synthesis of heteroaryl thioether in water media is developed. The reaction using alkyl halides and heteroaryl thiols as the starting materials can proceed well at room temperature for 0.5 h, affording the target thioether products in high yields. Compared with the available literature reports, this new method has the advantages of simple operation, mild conditions, less by-product, greeness and high efficiency, broad range of substrates, and etc. Moreover, the reaction can easily be scaled up in gram scale, also showing the good practical value of this new method. Mechanism studies suggested that both the tautomerism of mercaptopyridine to thiopyridone and the hydrogen bond and hydrophobic interaction of water played crucial roles in the reaction.

Key words: heteroaryl thioether, water media, base-free, mild conditions

Cite this article

Xiantao Ma, Xiaoyu Yan, Yingying Zhu, Shuanglin Niu, Yuxuan Wang, Chao Yuan. Water-Promoted Green Synthesis of Heteroaryl Thioether[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2136-2142.

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Fig. & Tab. 4

Scheme 1. Reports on the synthesis of heteroaryl thioether from alkyl halide and heteroaryl thiol

Entry	Solvent	Yield^b/%
1	H₂O	93
2	EtOH	81
3	Toluene	0
4	CHCl₃	0
5	EtOAc	0
6	MeCN	81
7	THF	0
8	DMF	90
9	DMSO	89
10^c	H₂O	92~95
11^d	MeCN, THF, etc.	67~84
12^e	H₂O	39

Table 1. Condition screening for the water-promoted synthesis of 2-(benzylthio)pyridine

Table 2. Substrate extension for the water-promoted synthesis of heteroaryl thioethers

Scheme 2. Possible reaction mechanism

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水促进下杂芳基硫醚的绿色合成

Water-Promoted Green Synthesis of Heteroaryl Thioether

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