Isoamyl Nitrite Activated Primary Sulfonamide to Sulfonyl Bromide and Sulfonyl Chloride

doi:10.6023/cjoc202310005

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (2): 533-549.DOI: 10.6023/cjoc202310005 Previous Articles Next Articles

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亚硝酸异戊酯活化伯磺酰胺制备磺酰溴与磺酰氯

江港钟, 林嘉欣, 鲍晓光^*(), 万小兵^*()

苏州大学材料与化学化工学部江苏苏州 215123

收稿日期:2023-10-07 修回日期:2023-11-02 发布日期:2023-11-07
基金资助:
国家自然科学基金(21973068); 国家自然科学基金(21971175)

Isoamyl Nitrite Activated Primary Sulfonamide to Sulfonyl Bromide and Sulfonyl Chloride

Gangzhong Jiang, Jiaxing Lin, Xiaoguang Bao(), Xiaobing Wan()

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123

Received:2023-10-07 Revised:2023-11-02 Published:2023-11-07
Contact: * E-mail: xgbao@suda.edu.cn; wanxb@suda.edu.cn
Supported by:
Natural Science Foundation of China(21973068); Natural Science Foundation of China(21971175)

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Abstract

Sulfonyl bromide and sulfonyl chloride are important compounds commonly used as building blocks in organic synthesis. This paper presents the successful synthesis of sulfonyl bromide or sulfonyl chloride from primary sulfonamide using isoamyl nitrite (ⁱAmONO) as an activator, dibromantine (DBDMH) as a bromine source, or trichloroisocyanuric acid (TCCA) as a chlorine source. The method offers several advantages such as wide range of raw materials, compatibility with various substrates, high yield, and mild reaction conditions. It is suitable for both gram-scale preparations and subsequent derivations, demonstrating practical value. Mechanistic studies suggest that N,N-dihalosulfonamide is a potential intermediate in this process and isoamyl nitrite plays a crucial role in the conversion process.

Key words: primary sulfonamide, isoamyl nitrite, sulfonyl bromide, sulfonyl chloride

Cite this article

Gangzhong Jiang, Jiaxing Lin, Xiaoguang Bao, Xiaobing Wan. Isoamyl Nitrite Activated Primary Sulfonamide to Sulfonyl Bromide and Sulfonyl Chloride[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 533-549.

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References 12

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Entry	Variation from the "standard conditions"	Yield^b/%
1	None	82
2	NBS instead of DBDMH	22
3	CBr₄ instead of DBDMH	N.d.
4	TBAB instead of DBDMH	N.d.
5	^tBuONO instead of ⁱAmONO	40
6	ⁿBuONO instead of ⁱAmONO	32
7	ⁱPrONO instead of ⁱAmONO	21
8	ⁱBuONO instead of ⁱAmONO	75
9	NaNO₂＋HCl instead of ⁱAmONO	50
10	CHCl₃ instead of DCM	58
11	DCE instead of DCM	35
12	DIOX instead of DCM	66
13	DMF instead of DCM	N.d.
14	MeOH instead of DCM	N.d.
15	O₂ instead of air	59
16	N₂ instead of air	42
17	No DBDMH^c	N.d.
18	No ⁱAmONO	N.d.

Entry	Variation from the "standard conditions"	Yield^b/%
1	None	82
2	NBS instead of DBDMH	22
3	CBr₄ instead of DBDMH	N.d.
4	TBAB instead of DBDMH	N.d.
5	^tBuONO instead of ⁱAmONO	40
6	ⁿBuONO instead of ⁱAmONO	32
7	ⁱPrONO instead of ⁱAmONO	21
8	ⁱBuONO instead of ⁱAmONO	75
9	NaNO₂＋HCl instead of ⁱAmONO	50
10	CHCl₃ instead of DCM	58
11	DCE instead of DCM	35
12	DIOX instead of DCM	66
13	DMF instead of DCM	N.d.
14	MeOH instead of DCM	N.d.
15	O₂ instead of air	59
16	N₂ instead of air	42
17	No DBDMH^c	N.d.
18	No ⁱAmONO	N.d.

Entry	Variation from the "standard conditions"	Yield^b/%
1	None	72
2	NCS instead of TCCA	48
3	DCDMH instead of TCCA	27
4	TCAB instead of TCCA	23
5	^tBuONO instead of ⁱAmONO	50
6	ⁿBuONO instead of ⁱAmONO	66
7	ⁱPrONO instead of ⁱAmONO	52
8	ⁱBuONO instead of ⁱAmONO	65
9	NaNO₂＋HCl instead of ⁱAmONO	Trace
10	DCM instead of CHCl₃	68
11	DCE instead of CHCl₃	63
12	MeCN instead of CHCl₃	65
13	EA instead of CHCl₃	Trace
14	MeOH instead of CHCl₃	N.d.
15	25 °C instead of 35 °C	65
16	3 h instead of 6 h	58
17	O₂ instead of air	63
18	N₂ instead of air	50
19	No TCCA	N.d.
20	No ⁱAmONO	N.d.

Entry	Variation from the "standard conditions"	Yield^b/%
1	None	72
2	NCS instead of TCCA	48
3	DCDMH instead of TCCA	27
4	TCAB instead of TCCA	23
5	^tBuONO instead of ⁱAmONO	50
6	ⁿBuONO instead of ⁱAmONO	66
7	ⁱPrONO instead of ⁱAmONO	52
8	ⁱBuONO instead of ⁱAmONO	65
9	NaNO₂＋HCl instead of ⁱAmONO	Trace
10	DCM instead of CHCl₃	68
11	DCE instead of CHCl₃	63
12	MeCN instead of CHCl₃	65
13	EA instead of CHCl₃	Trace
14	MeOH instead of CHCl₃	N.d.
15	25 °C instead of 35 °C	65
16	3 h instead of 6 h	58
17	O₂ instead of air	63
18	N₂ instead of air	50
19	No TCCA	N.d.
20	No ⁱAmONO	N.d.

亚硝酸异戊酯活化伯磺酰胺制备磺酰溴与磺酰氯

Isoamyl Nitrite Activated Primary Sulfonamide to Sulfonyl Bromide and Sulfonyl Chloride

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