立体位阻效应导致的苯酚的区域选择性溴化

doi:10.6023/cjoc201907038

有机化学 ›› 2019, Vol. 39 ›› Issue (10): 2796-2801.DOI: 10.6023/cjoc201907038 上一篇下一篇

研究论文

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)

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摘要/Abstract

报道了苯酚与廉价易得的氢溴酸的区域选择性溴化反应. 研究发现使用含有较大取代基的亚砜取代广为使用的二甲亚砜作为氧化剂, 可以极大地提高反应的区域选择性, 以中等至优秀的收率、高达99/1的区域选择性得到预期的溴代苯酚产物. 该方法可以很容易放大到50 mmol级别, 并且通过萃取与重结晶分离技术即可得到预期的溴代苯酚产物.

关键词: 苯酚, 区域选择性溴化, 氢溴酸, 亚砜, 位阻效应

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

引用此文

马献涛, 周坤洁, 任梦娟, 王梦雨, 于静. 立体位阻效应导致的苯酚的区域选择性溴化[J]. 有机化学, 2019, 39(10): 2796-2801.

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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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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