Functionalized Ionic Liquid [BMim]OH-Catalyzed the Synthesis of β-Ketosulfones and Sulfone Compounds between α-Halides and Sodium Sulfinate

doi:10.6023/cjoc202406010

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (1): 246-255.DOI: 10.6023/cjoc202406010 Previous Articles Next Articles

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功能化离子液体[BMim]OH催化α-卤代物与亚磺酸钠盐合成β-酮砜及砜类化合物

王浩洋, 成琳, 曾星, 韩利民, 杜玉英^*(), 竺宁^*()

内蒙古工业大学化工学院二氧化碳资源化利用自治区高等学校重点实验室内蒙古自治区CO₂捕集与资源化工程技术研究中心呼和浩特 010051

收稿日期:2024-06-08 修回日期:2024-08-03 发布日期:2024-08-30
基金资助:
内蒙古自治区自然科学基金(2023LHMS02011); 内蒙古自治区直属高校基本科研业务费(JY20240034); 内蒙古工业大学博士基金(BS2021023); 内蒙古自治区高等学校CO₂资源化利用创新团队(NMGIRT2212)

Functionalized Ionic Liquid [BMim]OH-Catalyzed the Synthesis of β-Ketosulfones and Sulfone Compounds between α-Halides and Sodium Sulfinate

Haoyang Wang, Lin Cheng, Xing Zeng, Limin Han, Yuying Du(), Ning Zhu()

Inner Mongolia Engineering Research Center for CO₂ Capture and Utilization, Key Laboratory of CO₂ Resource Utilization at Universities of Inner Mongolia Autonomous Region, College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051

Received:2024-06-08 Revised:2024-08-03 Published:2024-08-30
Contact: *E-mail: hhhtdyy@163.com; zhuning@imut.edu.cn
Supported by:
Natural Science Foundation of Inner Mongolia(2023LHMS02011); Fundamental Research Funds for the Inner Mongolia Autonomous Universities(JY20240034); Doctoral Funds of Inner Mongolia University of Technology(BS2021023); Innovative Research Team in Universities of Inner Mongolia Autonomous Region(NMGIRT2212)

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Abstract

The coupling reaction of α-halides and sodium sulfinate was catalyzed by functionalized ionic liquid [BMimlOH. 34 types β-ketone sulfones and sulfone compounds were obtained with medium to high yields (65%~99%) under mild and environmentally benign conditions. The reaction was scaled up to the gram scale, and [BMim]OH catalyst was recycled for 4 times without a significant decrease in yield. The results of ¹H NMR studies indicated that the initial event should be the catalytic interaction between [BMim]OH and the raw material sodium sulfite, leading to the formation of an intermediate [BMim][PhSO₂] in the reaction. Because the sulfur anion of intermediate had strong nucleophilicity, it reacted with α-bromoacetophenone which promoted the progress of the S_N2 reaction. The method offered advantages including simplicity of operation, stable and cycling catalyst, high yields, good functional group compatibility, metal-free catalysts, and environmental friendliness.

Key words: 1-butyl-3-methylimidazole hydroxide, catalysis, couple reaction, β-ketone sulfone and sulfones

Cite this article

Haoyang Wang, Lin Cheng, Xing Zeng, Limin Han, Yuying Du, Ning Zhu. Functionalized Ionic Liquid [BMim]OH-Catalyzed the Synthesis of β-Ketosulfones and Sulfone Compounds between α-Halides and Sodium Sulfinate[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 246-255.

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Entry	1a∶2a	[BMim]OH^a/%	T/℃	Solvent	Time/h	Yield^b/%
1	1∶1	—	r.t.	Ethanol (φ=50%)	2	45
2	1∶1	20	r.t.	Ethanol (φ=50%)	2	68
3	1∶1.2	20	r.t.	Ethanol (φ=50%)	2	79
4	1∶1.5	20	r.t.	Ethanol (φ=50%)	2	94 (80^c)
5	1∶2	20	r.t.	Ethanol (φ=50%)	2	95
6	1∶1.5	5	r.t.	Ethanol (φ=50%)	2	79
7	1∶1.5	10	r.t.	Ethanol (φ=50%)	2	86
8	1∶1.5	15	r.t.	Ethanol (φ=50%)	2	89
9	1∶1.5	30	r.t.	Ethanol (φ=50%)	2	95
10	1∶1.5	20	60	Ethanol (φ=50%)	1.5	98
11	1∶1.5	20	r.t.	H₂O	2	60
12	1∶1.5	20	r.t.	Anhydrous ethanol	2	65

Entry	1a∶2a	[BMim]OH^a/%	T/℃	Solvent	Time/h	Yield^b/%
1	1∶1	—	r.t.	Ethanol (φ=50%)	2	45
2	1∶1	20	r.t.	Ethanol (φ=50%)	2	68
3	1∶1.2	20	r.t.	Ethanol (φ=50%)	2	79
4	1∶1.5	20	r.t.	Ethanol (φ=50%)	2	94 (80^c)
5	1∶2	20	r.t.	Ethanol (φ=50%)	2	95
6	1∶1.5	5	r.t.	Ethanol (φ=50%)	2	79
7	1∶1.5	10	r.t.	Ethanol (φ=50%)	2	86
8	1∶1.5	15	r.t.	Ethanol (φ=50%)	2	89
9	1∶1.5	30	r.t.	Ethanol (φ=50%)	2	95
10	1∶1.5	20	60	Ethanol (φ=50%)	1.5	98
11	1∶1.5	20	r.t.	H₂O	2	60
12	1∶1.5	20	r.t.	Anhydrous ethanol	2	65

Entry	Catalyst	Condition	Time	Yield/%	Ref.
1	KI	V(AcOH)∶V(DMSO)=1∶1, 80 ℃	12 h	57 (3a)	[21]
2	CuBr₂	DMSO, r.t.	1 h	85 (3a)	[22]
3	Free Cat.	V(C₂H₅OH)∶V(H₂O)=3∶1, 50 ℃	10 h	65 (3m)	[23]
4	Mn, I₂	DMA, r.t.	24 h	80 (3a)	[24]
5	Cu_25%/ZIF-8	MeOH, r.t.	12 h	89 (3m)	[3]
6	Et₃N, I₂	H₂O	10 min	85 (3a)	[25]
7	PG(＋)\|St(－), KI, TBHP	MeOH, r.t.	10 h	82 (3a)	[5]
8	[BMim]OH	V(EtOH)∶V(H₂O)=1∶1, r.t.	2 h	94 (3a)	This work

Entry	Catalyst	Condition	Time	Yield/%	Ref.
1	KI	V(AcOH)∶V(DMSO)=1∶1, 80 ℃	12 h	57 (3a)	[21]
2	CuBr₂	DMSO, r.t.	1 h	85 (3a)	[22]
3	Free Cat.	V(C₂H₅OH)∶V(H₂O)=3∶1, 50 ℃	10 h	65 (3m)	[23]
4	Mn, I₂	DMA, r.t.	24 h	80 (3a)	[24]
5	Cu_25%/ZIF-8	MeOH, r.t.	12 h	89 (3m)	[3]
6	Et₃N, I₂	H₂O	10 min	85 (3a)	[25]
7	PG(＋)\|St(－), KI, TBHP	MeOH, r.t.	10 h	82 (3a)	[5]
8	[BMim]OH	V(EtOH)∶V(H₂O)=1∶1, r.t.	2 h	94 (3a)	This work

功能化离子液体[BMim]OH催化α-卤代物与亚磺酸钠盐合成β-酮砜及砜类化合物

Functionalized Ionic Liquid [BMim]OH-Catalyzed the Synthesis of β-Ketosulfones and Sulfone Compounds between α-Halides and Sodium Sulfinate

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