硫代磺酸酯和磺酰卤的绿色合成研究

doi:10.6023/cjoc202205010

摘要/Abstract

利用2-碘酰基苯甲酸(IBX)的氧化作用, 在四丁基溴化铵(TBAB)作为添加剂的条件下, 硫酚、硫醇类化合物在室温快速反应生成相应的硫代磺酸酯类化合物, 共获得了11个硫代磺酸酯, 产率为54%~83%; 而该氧化体系在加入浓盐酸(w=36%)或浓氢溴酸(w=46%)的条件下, 硫酚或硫醇均顺利被氧化卤代成相应的磺酰氯或磺酰溴, 分别获得了11个磺酰氯和11个磺酰溴产物, 产率为62%~84%. 这两种体系都简单、高效, 使用了绿色氧化剂和溶剂、具有处理简单、条件温和等优点, 所有合成产物均经¹H NMR、¹³C NMR结构确证.

关键词: 一锅法, 2-碘酰基苯甲酸(IBX), 卤化, 绿色合成

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

引用此文

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. 硫代磺酸酯和磺酰卤的绿色合成研究[J]. 有机化学, 2023, 43(1): 236-243.

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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参考文献 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