Citation: 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. doi: 10.6023/cjoc201907038 shu

Steric Hindrance Effect Leading to Regioselective Bromination of Phenols with HBr

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

Corresponding author: Ma Xiantao, xiantaoma@126.com
Received Date: 26 July 2019
Revised Date: 22 August 2019
Available Online: 5 October 2019
Fund Project: Project supported by the Key Scientific and Technological Project of Henan Province (No. 192102310031), the Scientific Research Project of Henan Province (No. 19B150018), the Nanhu Scholars Program for Young Scholars of Xinyang Normal University and the Young Core Instructor Program of Xinyang Normal University (No. 2018GGJS-05)the Key Scientific and Technological Project of Henan Province 192102310031the Young Core Instructor Program of Xinyang Normal University 2018GGJS-05the Scientific Research Project of Henan Province 19B150018

Figures(2)

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.
- phenol,
- regioselective bromation,
- HBr,
- sulfoxide,
- steric hindrance effect
1. [1]
  Fusetani, N.; Matsunaga, S. Chem. Rev. 1993, 93, 1793.
  (b) Segraves, E. N.; Shah, R. R.; Segraves, N. L.; Johnson, T. A.; Whitman, S.; Sui, J. K.; Kenyon, V. A.; Cichewicz, R. H.; Crews, P.; Holman, T. R. J. Med. Chem. 2004, 47, 4060.
  (c) Akai, S.; Kakiguchi, K.; Nakamura, Y.; Kuriwaki, I.; Dohi, T.; Harada, S.; Kubo, O.; Morita, N.; Kita, Y. Angew. Chem., Int. Ed. 2007, 46, 7458.
  (d) Qian, S.; Ma, Y.; Gao, S.; Luo, J. Chin. J. Org. Chem. 2018, 38, 1930(in Chinese).
  (钱少平, 马尧睿, 高姗姗, 骆钧飞, 有机化学, 2018, 38, 1930.)
  (e) Zhou, P.; Hou, A.; Wang, Y. Chin. J. Org. Chem. 2018, 38, 156(in Chinese).
  (周鹏飞, 侯爱君, 王洋, 有机化学, 2018, 38, 156.)
2. [2]
  For reviews: see: (a) Smith, K.; El-HitiI, G. A. Curr. Org. Synth. 2004, 1, 253.
  (b) Saikia, A. J.; Borah, P. P. Chem. Rev. 2016, 116, 6837.
3. [3]
  For a review, see: (a) Luo, J.; Xu, X.; Zhao, Y.; Liang, H. Chin. J. Org. Chem. 2017, 37, 2873(in Chinese).
  (骆钧飞, 徐星, 赵延超, 梁洪泽, 有机化学, 2017, 37, 2873.)
  For selected recent reports, see: (b) Okada, Y.; Yokozawa, M.; Akiba, M.; Oishi, K.; O-kawa, K.; Akeboshi, T.; Kawamura, Y.; Inokuma, S.; Nakamura, Y.; Nishimura, J. Org. Biomol. Chem. 2003, 1, 2506.
  (c) Bovonsombat, P.; Ali, R.; Khan, C.; Leykajarakul, J.; Pla-on, K.; Aphimanchindakul, S.; Pungcharoenpong, N.; Timsuea, N.; Arunrat, A.; Punpongjareorn, N. Tetrahedron 2010, 66, 6928.
  (d) Racys, D. T.; Warrilow, C. E.; Pimlott, S. L.; Sutherland, A. Org. Lett. 2015, 17, 4782.
  (e) Nishimura, J.; Tang, R.-J.; Milcent, T.; Crousse, B. J. Org. Chem. 2018, 83, 930.
4. [4]
  For a review, see: Vaillancourt, F. H.; Yeh, E.; Vosburg, D. A.; Garneau-Tsodikova, S.; Walsh, C. T. Chem. Rev. 2006, 106, 3364.
5. [5]
  For reviews, see: (a) Podgoršek, A.; Zupan, M.; Iskra, J. Angew. Chem., Int. Ed. 2009, 48, 8424.
  (b) Zhang, G.; Wang, Y.; Ding, C.; Liu, R.; Liang, X. Chin. J. Org. Chem. 2011, 31, 804(in Chinese).
  (张国富, 王涌, 丁成荣, 刘仁华, 梁鑫淼, 有机化学, 2011, 31, 804.)
  For selected recent reports, see: (c) Werf, A.; Selander, N. Org. Lett. 2015, 17, 6210.
  (d) Satkar, Y.; Ramadoss, V.; Nahide, P. D.; García-Medina, E.; Juárez-Ornelas, K. A.; Alonso-Castro, A. J.; Chávez-Rivera, R.; Jiménez-Halla, J. O. C.; Solorio-Alvarado, C. R. RSC Adv. 2018, 8, 17806.
  (e) Sorabad, G. S.; Maddani, M. R. New J. Chem. 2019, 43, 6563.
  (f) Walter, C.; Fallows, N.; Kesharwani, T. ACS Omega 2019, 4, 6538.
  (g) Semwal, R.; Ravi, C.; Kumar, R.; Meena, R.; Adimurthy, S. J. Org. Chem. 2019, 84, 792.
  (h) Satkar, Y.; Yera-Ledesma, L. F.; Mali, N.; Patil, D.; Navarro-Santos, P.; Segura-Quezada, L. A.; Ramírez-Morales, P. I.; Solorio-Alvarado, C. R. J. Org. Chem. 2019, 84, 4149.
  (i) Segura-Quezada, A.; Satkar, Y.; Patil, D.; Mali, N.; Wrobel, K.; González, G.; Zárraga, R.; Ortiz-Alvarado, R.; Solorio-Alvarado, C. R. Tetrahedron Lett. 2019, 60, 1551.
6. [6]
  For selected recent reports, see: (a) Mal, K.; Sharma, A.; Maulik, P. R.; Das, I. Chem.-Eur. J. 2013, 20, 662.
  (b) Liu, C.; Dai, R.; Yao, G.; Deng, Y. J. Chem. Res. 2014, 38, 593.
  (c) Song, S.; Li, X.; Sun, X.; Yuan, Y.; Jiao, N. Green Chem. 2015, 17, 3285.
  (d) Karki, M.; Magolan, J. J. Org. Chem. 2015, 80, 3701.
  (e) Mal, K.; Kaur, A.; Haque, F.; Das, I. J. Org. Chem. 2015, 80, 640.
  (f) Sorabad, G. S.; Maddani, M. R. New J. Chem. 2019, 43, 6563.
7. [7]
  (a) Pandit, P. K.; Gayen, S.; Khamarui, S.; Chatterjee, N.; Maiti, D. K. Chem. Commun. 2011, 47, 6933.
  (b) Iskra, J.; Murphree, S. S. Tetrahedron Lett. 2017, 58, 645.
  (c) Xin, H.; Yang, S.; An, B.; An, Z. RSC Adv. 2017, 7, 13467.
  (d) Tomizuka, A.; Moriyama, K. Adv. Synth. Catal. 2019, 361, 1447.
  (e) Xin, H.; Hu, L.; Yu, J.; Sun, W.; An, Z. Catal. Commun. 2017, 93, 1.
  (f) Kajita, H.; Togni, A. ChemistrySelect 2017, 2, 1117.
  (g) Cao, L.; Liu, B.; Liu, W.; Yao, G.; Cheng, Q. Chin. J. Org. Chem. 2011, 31, 2178(in Chinese).
  (曹志凌, 刘冰, 刘玮炜, 姚国伟, 程青芳, 有机化学, 2011, 31, 2178.)
8. [8]
  Song, S.; Sun, X.; Li, X.; Yuan, Y.; Jiao, N. Org. Lett. 2015, 17, 2886. doi: 10.1021/acs.orglett.5b00932
9. [9]
  For reviews, see: (a) Huang, Z.; Lumb, J.-P. ACS Catal. 2019, 9, 521.
  (b) Chen, Z.; Wang, B.; Zhang, J.; Yu, W.; Liu, Z.; Zhang, Y. Org. Chem. Front. 2015, 2, 1107.
  (c) Yanagi, T.; Nogi, K.; Yorimitsu, H. Tetrahedron Lett. 2018, 59, 2951.
10. [10]
  (a) Ma, X.-T.; Tian, S.-K. Adv. Synth. Catal. 2013, 355, 337.
  (b) Ma, X.; Yu, J.; Jiang, M.; Wang, M.; Tang, L.; Wei, M.; Zhou, Q. Eur. J. Org. Chem. 2019, 4593.
11. [11]
  Chauhan and coworkers reported a regioselective bromination of phenol with HBr at room temperature. The target 4-bromophenol could be obtained in 89% yield, but no experimental details could be found in the literature, see: Srivastava, S. K.; Chauhan, P. M. S.; Bhaduri, A. P. Chem. Commun. 1996, 2679 for details. We attempted for some times, but the target 3a was obtained only in low yield by using DMSO as a solvent at room temperature.
12. [12]
  Our experimental results are consistent with Jiao's observation, ie the use of stoichiometric DMSO as the oxidant instead of as the solvent can greatly improve the reaction efficiency and selectivity, see Ref. [8].
13. [13]
  Kakarla, R.; Dulina, R. G.; Hatzenbuhler, N. T.; Hui, Y. W.; Sofia, M. J. J. Org. Chem. 1996, 61, 8347. doi: 10.1021/jo961478h
14. [14]
  Choudhury, L. H.; Parvin, T.; Khan, A. T. Tetrahedron 2009, 65, 9513. doi: 10.1016/j.tet.2009.07.052
15. [15]
  Ghiaci, M.; Sedaghat, M. E.; Ranjbari, S.; Gil, A. Appl. Catal. A:Gen. 2010, 384, 18. doi: 10.1016/j.apcata.2010.05.053
16. [16]
  Mabic, S.; Lepoittevin, J.-P. Tetrahedron Lett. 1995, 36, 1705. doi: 10.1016/0040-4039(95)00050-M
17. [17]
  Lou, S.-J.; Chen, Q.; Wang, Y.-F.; Xu, D.-Q.; Du, X.-H.; He, J.-Q.; Mao, Y.-J.; Xu, Z.-Y. ACS Catal. 2015, 5, 2846. doi: 10.1021/acscatal.5b00306
18. [18]
  Xiong, X.; Yeung, Y.-Y. ACS Catal. 2018, 8, 4033. doi: 10.1021/acscatal.8b00327
19. [19]
  Carrigan, M. D.; Sarapa, D.; Smith, R. C.; Wieland, L. C.; Mohan, R. S. J. Org. Chem. 2002, 67, 1027. doi: 10.1021/jo016180s
20. [20]
  Yang, Y.; Lin, Y.; Rao, Y. Org. Lett. 2012, 14, 2874. doi: 10.1021/ol301104n
21. [21]
  Diemer, V.; Begaud, M.; Leroux, F. R.; Colobert, F. Eur. J. Org. Chem. 2011, 341.
22. [22]
  Kajita, H.; Togni, A. ChemistrySelect 2017, 2, 1117. doi: 10.1002/slct.201700024
23. [23]
  Kerr, D. J.; Willis, A. C.; Flynn, B. L. Org. Lett. 2004, 6, 457. doi: 10.1021/ol035822q
24. [24]
  Liu, Y.; Kim, J.; Seo, H.; Park, S.; Chae, J. Adv. Synth. Catal. 2015, 357, 2205. doi: 10.1002/adsc.201400941
1. [1]
  Shuang Li , Jiayu Sun , Guocheng Liu , Shuo Zhang , Zhong Zhang , Xiuli Wang . A new Keggin-type polyoxometallate-based bifunctional catalyst for trace detection and pH-universal photodegradation of phenol. Chinese Chemical Letters, 2024, 35(8): 109148-. doi: 10.1016/j.cclet.2023.109148
2. [2]
  Guanyang Zeng , Xingqiang Liu , Liangqiao Wu , Zijie Meng , Debin Zeng , Changlin Yu . Novel visible-light-driven I- doped Bi2O2CO3 nano-sheets fabricated via an ion exchange route for dye and phenol removal. Chinese Journal of Structural Chemistry, 2024, 43(12): 100462-100462. doi: 10.1016/j.cjsc.2024.100462
3. [3]
  Wujun Jian , Mong-Feng Chiou , Yajun Li , Hongli Bao , Song Yang . Cu-catalyzed regioselective diborylation of 1,3-enynes for the efficient synthesis of 1,4-diborylated allenes. Chinese Chemical Letters, 2024, 35(5): 108980-. doi: 10.1016/j.cclet.2023.108980
4. [4]
  Jun-Yi Wang , Jue-Yu Bao , Zheng-Guang Wu , Zheng-Yin Du , Xunwen Xiao , Xu-Feng Luo . Recent progress in steric modulation of MR-TADF materials and doping concentration independent OLEDs with narrowband emission. Chinese Journal of Structural Chemistry, 2025, 44(1): 100451-100451. doi: 10.1016/j.cjsc.2024.100451
5. [5]
  Fanxin Kong , Hongzhi Wang , Huimei Duan . Inhibition effect of sulfation on Pt/TiO2 catalysts in methane combustion. Chinese Journal of Structural Chemistry, 2024, 43(5): 100287-100287. doi: 10.1016/j.cjsc.2024.100287
6. [6]
  Min Fu , Pan He , Sen Zhou , Wenqiang Liu , Bo Ma , Shiying Shang , Yaohao Li , Ruihan Wang , Zhongping Tan . An unexpected stereochemical effect of thio-substituted Asp in native chemical ligation. Chinese Chemical Letters, 2024, 35(8): 109434-. doi: 10.1016/j.cclet.2023.109434
7. [7]
  Yixia Zhang , Caili Xue , Yunpeng Zhang , Qi Zhang , Kai Zhang , Yulin Liu , Zhaohui Shan , Wu Qiu , Gang Chen , Na Li , Hulin Zhang , Jiang Zhao , Da-Peng Yang . Cocktail effect of ionic patch driven by triboelectric nanogenerator for diabetic wound healing. Chinese Chemical Letters, 2024, 35(8): 109196-. doi: 10.1016/j.cclet.2023.109196
8. [8]
  Yuan Dong , Mutian Ma , Zhenyang Jiao , Sheng Han , Likun Xiong , Zhao Deng , Yang Peng . Effect of electrolyte cation-mediated mechanism on electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2024, 35(7): 109049-. doi: 10.1016/j.cclet.2023.109049
9. [9]
  Botao Gao , He Qi , Hui Liu , Jun Chen . Role of polarization evolution in the hysteresis effect of Pb-based antiferroelecrtics. Chinese Chemical Letters, 2024, 35(4): 108598-. doi: 10.1016/j.cclet.2023.108598
10. [10]
  Xin Huang , Yi Zhao , Wanzhen Liang . Vibronic coupling effect on intersystem crossing rates of TADF emitters. Chinese Journal of Structural Chemistry, 2024, 43(6): 100278-100278. doi: 10.1016/j.cjsc.2024.100278
11. [11]
  Cunjun Li , Wencong Liu , Xianlei Chen , Liang Li , Shenyu Lan , Mingshan Zhu . Adsorption and activation of peroxymonosulfate on BiOCl for carbamazepine degradation: The role of piezoelectric effect. Chinese Chemical Letters, 2024, 35(10): 109652-. doi: 10.1016/j.cclet.2024.109652
12. [12]
  Ziyou Zhang , Te Ji , Hongliang Dong , Zhiqiang Chen , Zhi Su . Effect of coordination restriction on pressure-induced fluorescence evolution. Chinese Chemical Letters, 2024, 35(12): 109542-. doi: 10.1016/j.cclet.2024.109542
13. [13]
  Shaohua Zhang , Xiaojuan Dai , Wei Hao , Liyao Liu , Yingqiao Ma , Ye Zou , Jia Zhu , Chong-an Di . A first-principles study of the Nernst effect in doped polymer. Chinese Chemical Letters, 2024, 35(12): 109837-. doi: 10.1016/j.cclet.2024.109837
14. [14]
  Xingxing Jiang , Yuxin Zhao , Yan Kong , Jianju Sun , Shangzhao Feng , Xin Lu , Qi Hu , Hengpan Yang , Chuanxin He . Support effect and confinement effect of porous carbon loaded tin dioxide nanoparticles in high-performance CO₂ electroreduction towards formate. Chinese Chemical Letters, 2025, 36(1): 109555-. doi: 10.1016/j.cclet.2024.109555
15. [15]
  Mingxin Song , Lijing Xie , Fangyuan Su , Zonglin Yi , Quangui Guo , Cheng-Meng Chen . New insights into the effect of hard carbons microstructure on the diffusion of sodium ions into closed pores. Chinese Chemical Letters, 2024, 35(6): 109266-. doi: 10.1016/j.cclet.2023.109266
16. [16]
  Chaochao Wei , Ru Wang , Zhongkai Wu , Qiyue Luo , Ziling Jiang , Liang Ming , Jie Yang , Liping Wang , Chuang Yu . Revealing the size effect of FeS₂ on solid-state battery performances at different operating temperatures. Chinese Chemical Letters, 2024, 35(6): 108717-. doi: 10.1016/j.cclet.2023.108717
17. [17]
  Chenlu Huang , Xinyu Yang , Qingyu Yu , Linhua Zhang , Dunwan Zhu . Gas-generating polymersomes-based amplified photoimmunotherapy for abscopal effect and tumor metastasis inhibition. Chinese Chemical Letters, 2024, 35(6): 109680-. doi: 10.1016/j.cclet.2024.109680
18. [18]
  Junchen Peng , Xue Yin , Dandan Dong , Zhongyuan Guo , Qinqin Wang , Minmin Liu , Fei He , Bin Dai , Chaofeng Huang . Promotion effect of epoxy group neighboring single-atom Cu site on acetylene hydrochlorination. Chinese Chemical Letters, 2024, 35(6): 109508-. doi: 10.1016/j.cclet.2024.109508
19. [19]
  Ting-Ting Huang , Jin-Fa Chen , Juan Liu , Tai-Bao Wei , Hong Yao , Bingbing Shi , Qi Lin . A novel fused bi-macrocyclic host for sensitive detection of Cr₂O₇²⁻ based on enrichment effect. Chinese Chemical Letters, 2024, 35(7): 109281-. doi: 10.1016/j.cclet.2023.109281
20. [20]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(1554)
HTML views(140)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142