无碱条件下直接多组分反应选择性合成非对称含氮杂芳基硫醚

doi:10.6023/cjoc202008030

有机化学 ›› 2021, Vol. 41 ›› Issue (3): 1193-1199.DOI: 10.6023/cjoc202008030 上一篇下一篇

研究论文

无碱条件下直接多组分反应选择性合成非对称含氮杂芳基硫醚

王琦^a, 朱柏燃^a, 杨光^a, 马献涛^a^,^b^,^*(), 徐清^a^,^c^,^*()

a 扬州大学化学化工学院江苏扬州 225002
b 信阳师范学院化学化工学院河南信阳 464000
c 温州大学化学与材料工程学院浙江温州 325035

收稿日期:2020-08-17 修回日期:2020-10-04 发布日期:2020-10-28
通讯作者: 马献涛, 徐清
基金资助:
国家自然科学基金(21672163); 扬州大学研究生科研创新计划(XKYCX19_064); 河南省科技攻关(192102310031)

Selective Synthesis of Unsymmetrical N-Heteroaryl Thioethers byBase-Free Direct Multi-Component Reaction

Qi Wang^a, Boran Zhu^a, Guang Yang^a, Xiantao Ma^a^,^b^,^*(), Qing Xu^a^,^c^,^*()

a School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002
b College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang, Henan 464000
c College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035

Received:2020-08-17 Revised:2020-10-04 Published:2020-10-28
Contact: Xiantao Ma, Qing Xu
About author:
* Corresponding authors. E-mail: xiantaoma@126.com;
xuqing@yzu.edu.cn, qing-xu@wzu.edu.cn
Supported by:
National Natural Science Foundation of China(21672163); Graduate Research and Innovation Program of Yangzhou University(XKYCX19_064); Key Scientific and Technological Project of Henan Province(192102310031)

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摘要/Abstract

杂芳基硫醚, 尤其是烷基杂芳基硫醚, 一般通过强碱性条件下的催化或非催化偶联方法来合成, 缺点多, 废弃物多. 本文报道一种卤代含氮杂芳烃、硫脲及溴代烷烃在无碱、无添加剂及无溶剂条件下的一锅多组分反应直接合成杂芳基硫醚的新方法. 本方法以硫脲为硫源, 并可兼容各种卤代含氮杂芳烃和溴代烷烃, 提供了一种含氮杂芳基硫醚的简洁、高效、选择性合成新方法.

关键词: 含氮杂芳基硫醚, 无碱, 硫脲, 硫转移, 多组分反应

Heteroaryl thioethers, especially alkyl heteroaryl thioethers, were usually obtained by catalytic or non-catalytic coupling reactions under strong basic conditions, but these methods usually have many drawbacks such as generation of large amounts of wastes. In this work, a new method for the direct synthesis of N-heteroaryl thioethers through a base-, additive-, and solvent-free one-pot multi-component reaction of N-heteroaryl halides, thiourea, and alkyl bromides was reported. This method can employ thiourea as the sulfur surrogate and tolerate various alkyl bromides and N-heteroaryl halides, providing a concise, selective, and efficient new method for heteroaryl thioether synthesis.

Key words: N-heteroaryl thioethers, base-free, thiourea, sulfur transfer, multi-component reaction

引用此文

王琦, 朱柏燃, 杨光, 马献涛, 徐清. 无碱条件下直接多组分反应选择性合成非对称含氮杂芳基硫醚[J]. 有机化学, 2021, 41(3): 1193-1199.

Qi Wang, Boran Zhu, Guang Yang, Xiantao Ma, Qing Xu. Selective Synthesis of Unsymmetrical N-Heteroaryl Thioethers byBase-Free Direct Multi-Component Reaction[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1193-1199.

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Entry	Base (equiv.)	Solvent (mL)	T., t	Yield^b/%
1	Bases^c (2)	None	140 ℃, 24 h	Trace~35
2	None	None	140 ℃, 24 h	33
3	None	None	(i) 80 ℃, 1 h; (ii) 140 ℃, 24 h	43 (A)^d
4	None	None	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	59 (A)^d
5	None	None	(i) 80 ℃, 1 h; (i) 170 ℃, 24 h	69 (A)^d^,^e
6	None	CH₃CN (1)	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	21 (A)^d^,^e
7	None	EtOH (1)	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	10 (A)^d^,^e
8	None	None	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	61 (B)^e^,^f

Entry	Base (equiv.)	Solvent (mL)	T., t	Yield^b/%
1	Bases^c (2)	None	140 ℃, 24 h	Trace~35
2	None	None	140 ℃, 24 h	33
3	None	None	(i) 80 ℃, 1 h; (ii) 140 ℃, 24 h	43 (A)^d
4	None	None	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	59 (A)^d
5	None	None	(i) 80 ℃, 1 h; (i) 170 ℃, 24 h	69 (A)^d^,^e
6	None	CH₃CN (1)	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	21 (A)^d^,^e
7	None	EtOH (1)	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	10 (A)^d^,^e
8	None	None	(i) 80 ℃, 1 h; (ii) 170 ℃, 24 h	61 (B)^e^,^f

无碱条件下直接多组分反应选择性合成非对称含氮杂芳基硫醚

Selective Synthesis of Unsymmetrical N-Heteroaryl Thioethers byBase-Free Direct Multi-Component Reaction

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