Green Synthesis of Thiosulfonates and Sulfonyl Halides

doi:10.6023/cjoc202205010

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (1): 236-243.DOI: 10.6023/cjoc202205010 Previous Articles Next Articles

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硫代磺酸酯和磺酰卤的绿色合成研究

乃比江•赛米, 张蕾, 买地娜•沙拉木, 曾竟^*(), 阿布都热西提•阿布力克木^*()

新疆师范大学化学系乌鲁木齐 830054

收稿日期:2022-05-07 修回日期:2022-08-01 发布日期:2022-08-25
通讯作者: 曾竟, 阿布都热西提•阿布力克木
基金资助:
新疆维吾尔自治区高校科研计划自然科学重点(XJEDU2020I015)

Green Synthesis of Thiosulfonates and Sulfonyl Halides

Saimi Naibijiang, Lei Zhang, Shalamu Maidina, Jing Zeng(), Abudu Rexit Abulikemu()

Department of Chemistry, Xinjiang Normal University, Urumqi 830054

Received:2022-05-07 Revised:2022-08-01 Published:2022-08-25
Contact: Jing Zeng, Abudu Rexit Abulikemu
Supported by:
Scientific Research Program of the Higher Education Institution of Xinjiang(XJEDU2020I015)

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Abstract

Using the oxidation between 2-iodoylbenzoic acid (IBX) and tetrabutylammonium bromide (TBAB), thiophenols and thiols reacted rapidly to form corresponding thiosulfonates at room temperature, and 11 thiosulfonates were obtained with yields ranging from 54% to 83%. It was also found that the catalytic system in the presence of aqueous HCl (w=36%) and HBr (w=46%) oxidatively halogenated thiophenols and thiols, respectively, 11 kinds of sulfonyl chlorides and 11 kinds of sulfonyl bromides were obtained with yields ranging from 62% to 84%. The method has the advantages of simple and efficient, simple post-treatment, green oxidant and solvent, mild conditions, etc. All products were confirmed by ¹H NMR, ¹³C NMR structure.

Key words: one-pot reaction, 2-iodoylbenzoic acid (IBX), halogenation, green synthesis

Cite this article

Saimi Naibijiang, Lei Zhang, Shalamu Maidina, Jing Zeng, Abudu Rexit Abulikemu. Green Synthesis of Thiosulfonates and Sulfonyl Halides[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 236-243.

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Fig. & Tab. 5

References 21

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Entry	Oxidant (equiv.)	Additive (equiv.)	Solvent	Time/h	Yield^b/% of 2a	Yield^b/% of 3a
1	TBHP (2.0)	—	CH₂Cl₂	24	86	Trace
2	H₂O₂ (10)	—	CH₂Cl₂	24	88	0
3	PCC (2.0)	—	CH₂Cl₂	24	78	Trace
4	KMnO₄ (1.0)	—	CH₂Cl₂	24	90	0
5	NaClO (2.0)	—	CH₂Cl₂	24	65	0
6	BPD (2.0)	—	CH₂Cl₂	16	76	21
7	DDQ (2.0)	—	CH₂Cl₂	16	88	Trace
8	Ag₂O (2.0)	—	CH₂Cl₂	18	75	17
9	IBX (1.0)	—	CH₂Cl₂	24	58	42
10	IBX (1.0)	—	THF	8	57	Trace
11	IBX (1.0)	—	DMF	9	0	38
12	IBX (1.0)	—	DMSO	9	0	46
13	IBX (1.0)	—	TBA	6	49	0
14	IBX (1.0)	—	PhMe	6	63	0
15	IBX (1.0)	—	CH₃CN	9	25	61
16	IBX (1.0)	TBAB (0.1)	CH₃CN	4.5	0	69
17	IBX (1.0)	TBAB (0.12)	CH₃CN	4	0	73
18	IBX (1.0)	TBAB (0.15)	CH₃CN	3	0	71
19	IBX (1.2)	TBAB (0.12)	CH₃CN	4	0	83
20	IBX (1.2)	TEAB (0.12)	CH₃CN	6	0	65
21	IBX (0.2)	TBAB (0.02)	CH₃CN	1	94	0
22	IBX (0.5)	TBAB (0.05)	CH₃CN	1	90	Trace

Entry	Oxidant (equiv.)	Additive (equiv.)	Solvent	Time/h	Yield^b/% of 2a	Yield^b/% of 3a
1	TBHP (2.0)	—	CH₂Cl₂	24	86	Trace
2	H₂O₂ (10)	—	CH₂Cl₂	24	88	0
3	PCC (2.0)	—	CH₂Cl₂	24	78	Trace
4	KMnO₄ (1.0)	—	CH₂Cl₂	24	90	0
5	NaClO (2.0)	—	CH₂Cl₂	24	65	0
6	BPD (2.0)	—	CH₂Cl₂	16	76	21
7	DDQ (2.0)	—	CH₂Cl₂	16	88	Trace
8	Ag₂O (2.0)	—	CH₂Cl₂	18	75	17
9	IBX (1.0)	—	CH₂Cl₂	24	58	42
10	IBX (1.0)	—	THF	8	57	Trace
11	IBX (1.0)	—	DMF	9	0	38
12	IBX (1.0)	—	DMSO	9	0	46
13	IBX (1.0)	—	TBA	6	49	0
14	IBX (1.0)	—	PhMe	6	63	0
15	IBX (1.0)	—	CH₃CN	9	25	61
16	IBX (1.0)	TBAB (0.1)	CH₃CN	4.5	0	69
17	IBX (1.0)	TBAB (0.12)	CH₃CN	4	0	73
18	IBX (1.0)	TBAB (0.15)	CH₃CN	3	0	71
19	IBX (1.2)	TBAB (0.12)	CH₃CN	4	0	83
20	IBX (1.2)	TEAB (0.12)	CH₃CN	6	0	65
21	IBX (0.2)	TBAB (0.02)	CH₃CN	1	94	0
22	IBX (0.5)	TBAB (0.05)	CH₃CN	1	90	Trace

Entry	IBX/equiv.	TBAB (equiv.)	Halogen source (equiv.)	Solvent	Time/min	Yield^b/%
1	2.0	TBAB (0.2)	SOCl₂ (3)	CH₃CN	15	63
2	2.0	TBAB (0.2)	(COCl)₂ (3)	CH₃CN	15	67
3	2.0	TBAB (0.2)	POCl₃(3)	CH₃CN	15	62
4	2.0	TBAB (0.2)	HCl (5)	CH₃CN	20	67
5	2.0	TBAB (0.2)	HCl (10)	CH₃CN	15	69
6	2.0	TBAB (0.2)	HCl (15)	CH₃CN	10	75
7	2.0	TBAB (0.2)	HCl (20)	CH₃CN	10	68
8	1.0	TBAB (0.2)	HCl (15)	CH₃CN	15	34
9	2.5	TBAB (0.2)	HCl (15)	CH₃CN	10	62
10	2.0	TBAB (0.1)	HCl (15)	CH₃CN	15	64
11	2.0	TBAB (0.3)	HCl (15)	CH₃CN	10	61
12	2.0	TBAB (0.2)	HCl (15)	THF	25	31
13	2.0	TBAB (0.2)	HCl (15)	EtOAc	10	77
14	2.0	TBAB (0.2)	HCl (15)	PhMe	10	53
15	2.0	TBAB (0.2)	HCl (15)	2-MeTHF	25	28
16	2.0	TBAB (0.2)	HCl (15)	CH₂Cl₂	10	73
17	2.0	TBAB (0.2)	HCl (15)	EtOH	10	35

Entry	IBX/equiv.	TBAB (equiv.)	Halogen source (equiv.)	Solvent	Time/min	Yield^b/%
1	2.0	TBAB (0.2)	SOCl₂ (3)	CH₃CN	15	63
2	2.0	TBAB (0.2)	(COCl)₂ (3)	CH₃CN	15	67
3	2.0	TBAB (0.2)	POCl₃(3)	CH₃CN	15	62
4	2.0	TBAB (0.2)	HCl (5)	CH₃CN	20	67
5	2.0	TBAB (0.2)	HCl (10)	CH₃CN	15	69
6	2.0	TBAB (0.2)	HCl (15)	CH₃CN	10	75
7	2.0	TBAB (0.2)	HCl (20)	CH₃CN	10	68
8	1.0	TBAB (0.2)	HCl (15)	CH₃CN	15	34
9	2.5	TBAB (0.2)	HCl (15)	CH₃CN	10	62
10	2.0	TBAB (0.1)	HCl (15)	CH₃CN	15	64
11	2.0	TBAB (0.3)	HCl (15)	CH₃CN	10	61
12	2.0	TBAB (0.2)	HCl (15)	THF	25	31
13	2.0	TBAB (0.2)	HCl (15)	EtOAc	10	77
14	2.0	TBAB (0.2)	HCl (15)	PhMe	10	53
15	2.0	TBAB (0.2)	HCl (15)	2-MeTHF	25	28
16	2.0	TBAB (0.2)	HCl (15)	CH₂Cl₂	10	73
17	2.0	TBAB (0.2)	HCl (15)	EtOH	10	35

硫代磺酸酯和磺酰卤的绿色合成研究

Green Synthesis of Thiosulfonates and Sulfonyl Halides

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