Steric Hindrance Effect Leading to Regioselective Bromination of Phenols with HBr

doi:10.6023/cjoc201907038

Chinese Journal of Organic Chemistry ›› 2019, Vol. 39 ›› Issue (10): 2796-2801.DOI: 10.6023/cjoc201907038 Previous Articles Next Articles

ARTICLE

立体位阻效应导致的苯酚的区域选择性溴化

马献涛^*(), 周坤洁, 任梦娟, 王梦雨, 于静

信阳师范学院化学化工学院信阳 464000

收稿日期:2019-07-26 修回日期:2019-08-22 发布日期:2019-09-05
通讯作者: 马献涛 E-mail:xiantaoma@126.com
基金资助:
河南省科技攻关(192102310031);河南省高等学校重点科研(19B150018);信阳师范学院“南湖学者奖励计划”青年项目;信阳师范学院青年骨干教师计划资助项目(2018GGJS-05)

Steric Hindrance Effect Leading to Regioselective Bromination of Phenols with HBr

Ma Xiantao^*(), Zhou Kunjie, Ren Mengjuan, Wang Mengyu, Yu Jing

College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000

Received:2019-07-26 Revised:2019-08-22 Published:2019-09-05
Contact: Ma Xiantao E-mail:xiantaoma@126.com
Supported by:
Project supported by the Key Scientific and Technological Project of Henan Province(192102310031);The Scientific Research Project of Henan Province(19B150018);The Nanhu Scholars Program for Young Scholars of Xinyang Normal University;The Young Core Instructor Program of Xinyang Normal University(2018GGJS-05)

A mild and regioselective bromination of phenols with the cheap and easily-available HBr is developed. By replacing the common used dimethyl sulfoxide (DMSO) with sulfoxides bearing sterically hindered substituents, the desired brominated phenols could be obtained in moderate to high yields with up to 99/1 regioselectivity. This method could be easily scaled up to 50 mmol scale and has the potential to isolate the desired product by simple extraction and recrystallization, showing great practicality of this new method.

Key words: phenol, regioselective bromation, HBr, sulfoxide, steric hindrance effect

Cite this article

Ma Xiantao, Zhou Kunjie, Ren Mengjuan, Wang Mengyu, Yu Jing. Steric Hindrance Effect Leading to Regioselective Bromination of Phenols with HBr[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2796-2801.

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Fig. & Tab. 4

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Entry	R (2)	Solvent	3a^b/%	3a/4a^c
1^d	Me (2a)	DMSO	25	61/39
2	Me (2a)	DMSO	55	69/31
3	Me (2a)	MeCN	80	89/11
4	n-Bu (2b)	MeCN	75	93/7
5	Bn (2c)	MeCN	82	98/2
6	Ph (2d)	MeCN	86	95/5
7	4-MeC₆H₄ (2e)	MeCN	87	96/4
8	4-ClC₆H₄ (2f)	MeCN	91	97/3
9	4-ClC₆H₄ (2f)	EtOAc	84	94/6
10	4-ClC₆H₄ (2f)	DMF	0	—
11	4-ClC₆H₄ (2f)	CHCl₃	41	62/38

Entry	R (2)	Solvent	3a^b/%	3a/4a^c
1^d	Me (2a)	DMSO	25	61/39
2	Me (2a)	DMSO	55	69/31
3	Me (2a)	MeCN	80	89/11
4	n-Bu (2b)	MeCN	75	93/7
5	Bn (2c)	MeCN	82	98/2
6	Ph (2d)	MeCN	86	95/5
7	4-MeC₆H₄ (2e)	MeCN	87	96/4
8	4-ClC₆H₄ (2f)	MeCN	91	97/3
9	4-ClC₆H₄ (2f)	EtOAc	84	94/6
10	4-ClC₆H₄ (2f)	DMF	0	—
11	4-ClC₆H₄ (2f)	CHCl₃	41	62/38

立体位阻效应导致的苯酚的区域选择性溴化

Steric Hindrance Effect Leading to Regioselective Bromination of Phenols with HBr

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