SIOC 中文
CJOG
Adv search

Chinese Journal of Organic Chemistry >

0 202606025 - 202606025

DOI: https://doi.org/10.6023/cjoc202606025

REVIEW

Recent Advances in the Synthesis of 4,4′-biphenol

  • Zhang Huaiyuan ,
  • Wang Xiyue ,
  • Liu Rong ,
  • Liang Chaorong ,
  • Zhang Qiguo ,
  • Liu Rongrong ,
  • Chen Ziwei ,
  • Liang Mingyu
Expand
  • aSchool of Applied Chemical Engineering, Lanzhou Petrochemical University of Vocational Technology, Lanzhou 730060;
    bGansu Research Institute of Chemical Industry Co., Ltd. Lanzhou 730020

Received date: 2026-06-21

  Revised date: 2026-08-16

  Online published: 2026-09-16

Supported by

The Scientific Research Project of the Education Department of Gansu Province(No. 2026CYZC-071).

Fold

Abstract

4,4′-Biphenol is a key basic raw material for the synthesis of advanced polymers, resins, and specialty materials. It possesses excellent thermal stability, chemical resistance, and mechanical strength, and can be used as a modifying monomer in polyesters, polyurethanes, epoxy resins, liquid crystal materials, as well as in the synthesis of pharmaceuticals and pesticides. The compound contains two phenolic hydroxyl groups in its structure, which can undergo various reactions such as substitution and oxidation, leading to many derivatives. Although 4,4′-biphenol is widely used across multiple industries, high-purity (99.5%) product is still entirely dependent on imports, and its synthesis faces significant challenges. This review takes the synthetic raw materials as the main thread and systematically summarizes various synthetic routes, which are mainly classified into four categories: oxidative coupling of phenolic compounds, functional group transformation using biphenyl compounds as the skeleton, construction of the biphenyl structure from 4-hydroxyphenyl derivatives, and methods involving other substrates, aiming to provide a reference for the synthesis research of high-purity 4,4′-biphenol.

Key words： 4,4'-Biphenol; oxidative coupling; reductive elimination; synthetic method

Cite this article

Zhang Huaiyuan , Wang Xiyue , Liu Rong , Liang Chaorong , Zhang Qiguo , Liu Rongrong , Chen Ziwei , Liang Mingyu . Recent Advances in the Synthesis of 4,4′-biphenol[J]. Chinese Journal of Organic Chemistry, 0 : 202606025 -202606025 . DOI: 10.6023/cjoc202606025

References

[1] (a) Yoshioka T.; Motoki T.; Okuwaki, A. Ind. Eng. Chem. Res.2001, 40, 75-79.
(b) Hira; Ali F.; Waqar M.; Cheong W. J.; Munazzah; AlOthman, Z. A. RSC Adv.2026, 16, 5956-5969.
[2] (a) Grause G.; Kaminsky W.; Fahrbach, G. Polym. Degrad. Stab.2004, 85, 571-575.
(b) Blaser, H. U.; Schmidt, E. Asymmetric Catalysis on Industrial Scale. Challenges, Approaches and Solutions, Wiley-VCH, Weinheim, 2004.
[3] Khan B.; Khalid M.; Shah M. R.; Tahir M. N.; Khan M. U.; Ali A.; Muhammad S. ChemistrySelect2019, 4, 9274-9284.
[4] (a) Goje A. S.; Thakur S. A.; Diware V. R.; Chauhan Y. P.; Mishra S. Polym-Plast Technol.2004, 43, 369-388.
(b) Jia Y.; Guan Q.; Chu C.; Zhang L.; Neisiany R. E.; Gu S.; Sun J.; You Z. Sci. Bull.2024, 69, 1875-1886.
(c) Nematollahi, D.; Baniardalan, M.; Khazalpour, S.; Pajohi-Alamoti, M. R. Electrochim. Acta 2016, 191, 98-105.
[5] (a) Sivaramakrishnan T.; Annamalai G.; Elango, G. Asian J. Res. Chem.2020, 13, 103-108.
(b) Kalbende P. P.; Zade, A. B. J. Macromol. Sci. A2014, 51, 37-48.
(c) Rowlett, J. R.; Chen, Y.; Shaver, A. T.; Fahs, G. B.; Sundell, B. J.; Li, Q.; Kim, Y. S.; Zelenay, P.; Moore, R. B.; Mecham, S.; McGrath, J. E. J. Electrochem. Soc. 2014, 161, F535-F543.
[6] (a) Ogata M.; Shin-ya K.; Urano S.; Endo, T. Chem. Pharm. Bull.2005, 53, 344-346.
(b) Şentürk M.; Gülçin İ.; Daştan A.; Küfrevioğlu, Ő İ.; Supuran, C.T. Bioorg. Med. Chem.2009, 17, 3207-3211.
(c) Andiya-Pravdivyi, Y. E.; Bureeva, S. V.; Kaplun, A. P.; Shvets, V. I. Pharm. Chem. J. 2004, 38, 123-127.
[7] (a) Pang J.; Yuan S.; Du D.; Lollar C.; Zhang L.; Wu M.; Yuan D.; Zhou H.-C.; Hong, M. Angew. Chem. Int. Ed.2017, 56, 14622-14626.
(b) Zolfigol M. A.; Khazaei A.; Moosavi-Zare A. R.; Zare A.; Kruger H. G.; Asgari Z.; Khakyzadeh V.; Kazem-Rostami, M. J. Org. Chem.2012, 77, 3640-3645.
(c) Maegawa, T.; Akashi, A.; Yaguchi, K.; Iwasaki, Y.; Shigetsura, M.; Monguchi, Y.; Sajiki, H. Chem. Eur. J. 2009, 15, 6953-6963.
[8] (a) Zhang H.; Cormanich R. A.; Wirth, T. Chem. Eur. J.2022, 28, e202103623.
(b) Zhang, H.; Wirth, T.Chem. Eur. J. 2022, 28, e202200181.
(c) Zhang, H.; Xu, N.; Zhang, C.; Zhang, Z.; Tang, R.; Wang, S.; Xie, L. CN 118084850 B, 2026 (in Chinese).
(张怀远, 许诺, 张崇恩, 张志远, 唐蓉萍, 王守伟, 颉林. CN 118084850 B, 2026)
[9] Liu S.; Li X.; Chen B.; Ouyang X.; Xie Y.; Chen D. Molecules2022, 27, 4842.
[10] Kumar R.; Awasthi A.; Gupta S.; Eerlapally R.; Draksharapu A. Dalton Trans.2022, 51, 12848-12854.
[11] Lee J.; Kumar A.; Tüysüz, H. Angew. Chem. Int. Ed.2024, 63, e202404496.
[12] Yuan B.; Pan Y.; Li Y.; Yin B.; Jiang, H. Angew. Chem. Int. Ed.2010, 49, 4054-4058.
[13] Zhang Q.; Mao Z.; Wang K.; Phan N. T. S.; Zhang F. Green Chem.2020, 22, 3239-3247.
[14] Gallon B. J.; Kojima R.W.; Kaner R. B.; Diaconescu, P. L. Angew. Chem. Int. Ed.2007, 46, 7251-7254.
[15] Chen Y.; Peng H.; Pi Y.-X.; Meng T.; Lian Z.-Y.; Yan M.-Q.; Liu Y.; Liu S.-H.; Yu, G.-A. Org. Biomol. Chem.2015, 13, 3236-3242.
[16] Sengupta D.; Pandey M. K.; Mondal D.; Radhakrishna L.; Balakrishna, M. S. Eur. J. Inorg. Chem.2018, 2018, 3374-3383.
[17] Ji H.; Wu L.-Y.; Cai J.-H.; Li G.-R.; Gan N.-N.; Wang Z.-H. RSC Adv.2018, 8, 13643-13648.
[18] Wan Y.; Wang H.; Zhao Q.; Klingstedt M.; Terasaki O.; Zhao, D. J. Am. Chem. Soc.2009, 131, 4541-4550.
[19] Mukhopadhyay S.; Joshi A. V.; Peleg L.; Sasson, Y. Org. Process Res. Dev.2003, 7, 44-46.
[20] Colon I.; Kelsey, D. R. J. Org. Chem.1986, 51, 2627-2637.
[21] (a) Abiraj, K.; Srinivasa, G. R.; Gowda, D. C. Tetrahedron Lett. 2004, 45, 2081-2084.
(b) Abiraj K.; Srinivasa G. R.; Gowda D. C. Synlett2004, 5, 0877-0879.
[22] Du F.; Zhou Q.; Liu D.; Fang T.; Shi Y.; Du Y.; Chen G. Synlett2018, 29, 779-784.
[23] Abdollahi-Alibeik M.; Ramazani, Z. Main Group Met. Chem.2022, 45, 190-201.
[24] Han F.; Xia J.; Zhang X.; Fu Y. RSC Adv.2019, 9, 17812-17823.
[25] Courtois V.; Barhdadi R.; Troupel M.; Périchon J. Tetrahedron1997, 53, 11569-11576.
[26] Wang Z.-J.; Wang X.; Lv J.-J.; Feng J.; Xu X.; Wang A.-J.; Liang, Z. New J. Chem.2017, 41, 3894-899.
[27] Lourak M.; Vanderesse R.; Fort Y.; Caubère, P. J. Org. Chem.1989, 54, 4840-4844.
[28] Mhate M.; Khanra M.; Saharia N.; Radhakrishnanand P.; Ravichandiran V.; Swain, S. P. Appl. Organomet. Chem.2025, 39, e8006.
[29] Kuroboshi M.; Yamamoto T.; Tanaka H. Synlett2013, 24, 0197-0200.
[30] (a) Ram R. N.; Singh V. Tetrahedron Lett.2006, 47, 7625-7628.
(b) Busch V. M.; Weber, W. Journal F. Prakt. Chemie1936, 146, 23.
[31] Pachón L. D.; Elsevier C. J.; Rothenberg, G. Adv. Synth. Catal.2006, 348, 1705-1710.
[32] Patel B. P.; Pressman E. J.; Mills R. C.US 6833482, 2004.
[33] Tripathi J.; Gupta M.; Yadav A.; Waghmode K.; More, P. Res. Chem. Intermed.2024, 50, 1645-1660.
[34] Lourak M.; Vanderesse R.; Fort Y.; Caubère, P. J. Org. Chem.1989, 54, 4844-4848.
[35] Everson D. A.; Jones B. A.; Weix, D. J. J. Am. Chem. Soc.2012, 134, 6146-6159.
[36] Twitty J. C.; Hong Y.; Garcia B.; Tsang S.; Liao J.; Schultz D. M.; Hanisak J.; Zultanski S. L.; Dion A.; Kalyani D.; Watson, M. P. J. Am. Chem. Soc.2023, 145, 5684-5695.
[37] Andersen N. G.; Maddaford S. P.; Keay, B. A. J. Org. Chem.1996, 61, 9556-9559.
[38] Lee P. H.; Seomoon D.; Lee K. Org. Lett. 2005, 7, 343-345.
[39] Zhang D.; Zhang Q.; Zhang J.; Yan R.; Xu L. CN 111533645 B, 2022 (in Chinese).
(张东宝, 张奇, 张建民, 闫茹, 徐良.CN 111533645 B, 2022)
[40] Zhang D.; Yu R.; Xu L.CN 114031484 B, 2024 (in Chinese).
(张东宝, 于冉, 徐良.CN 114031484 B, 2024)
[41] Zhou Q.; Wang Y.-N.; Guo X.-Q.; Zhu X.-H.; Li Z.-M.; Hou X.-F. Organometallics2015, 6, 1021-1028.
[42] Wang G.; Wu Z.; Liang Y.; Liu W.; Zhan H.; Song M.; Sun Y. J. Catal.2020, 384, 177-188.
[43] Bao F.; Liu Z.; Bai H.; Zhang H.; Liu P.; Zhang Q.; Chai G. Synlett2020, 31, 1501-1506.
[44] Sagrera G.; Bertucci A.; Vazquez A.; Seoane, G. Bioorgan. Med. Chem.2011, 19, 3060-3073.
[45] Sapal V. B.; Saetta C.; Laufenböck A.; Sterrer M.; Kwon S. I.; Lucotti A.; Tommasini M.; Tomanec O.; Bakandritsos A.; Liberto G. D.; Pacchioni G.; Vilé, G. J. Am. Chem. Soc.2025, 147, 18524-18540.
[46] Garcia-Martinez J. C.; Lezutekong R.; Crooks, R. M. J. Am. Chem. Soc.2005, 127, 5097-5103.
[47] Karimi Zarchi, M. A.; Darbandizadeh Mohammad Abadi, S. S. A.Res. Chem. Intermed. 2019, 45, 2605-2639.
[48] Saki S.; Khodaei M. M.Inorg. Chem.Commun. 2025, 176, 114247.
[49] Schmidt B.; Riemer, M. J. Org. Chem.2014, 79, 4104-4118.
[50] (a) Keum D.; Kim S.; Kim Y. Chem. Commun.2014, 50, 1268-1270.
(b) Tang J.; Liu F.; Nagy E.; Miller L.; Kirby K. A.; Wilson D. J.; Wu B.; Sarafianos S. G.; Parniak M. A.; Wang, Z. J. Med. Chem.2016, 59, 2648-2659.
[51] Zeng T.M. Dissertation, Guangxi University, Nanning, 2015 (in Chinese).
(曾涛. 硕士论文, 广西大学, 南宁, 2015)
[52] Zhao Y.M. Dissertation, Dalian University of Technology, Dalian, 2024 (in Chinese).
(赵玉倩. 硕士论文, 大连理工大学, 大连, 2024)
[53] Zhou M.; Sun J.; Pang W.; Wang J.; Chen Y.CN 116178111 B, 2025 (in Chinese).
(周明东, 孙京, 庞威军, 王景芸, 陈阳.CN 116178111 B, 2025)
[54] Fu Z.; Gao T.; Ma N.; Pan X.; Yu W.; Guo Y.CN 117776875 A, 2024 (in Chinese).
(傅志伟, 高天伟, 马宁泽, 潘新刚, 余文卿, 郭有壹.CN 117776875 A, 2024)
[55] Gregory K.WO. 2004/018401 A1, 2004.
[56] Ma L.; Chen J.; Liu T.; Xu J.; Zhang C.; Li N.; Wang J.CN 118724784 B, 2024 (in Chinese).
(马龙龙, 陈建华, 刘天琪, 徐杰, 张成龙, 李宁, 王金亭.CN 118724784 B, 2024)
[57] Dong J.; Zhou M.; Jiang L.; Sun J.; Liu S.; Teng J.CN 119954613 A, 2025 (in Chinese).
(董静, 周明东, 姜丽燕, 孙京, 刘苏, 滕加伟.CN 119954613 A, 2025)
[58] Olah G. A.; Prakash G. K. S.; Iyer P. S.; Tashiro M.; Yamato T.; J. Org. Chem.1987, 52, 1881-1884.
[59] Tong Z.-B.; Ren G.-D.Fine Chemicals 1999, 16, 34-36 (in Chinese).
(童志彪, 任国度. 精细化工, 1999, 16, 34-36).
[60] Zhong Z.; Mi X.; Kong Y.; Yang H.CN 109896925 A, 2019 (in Chinese).
(钟铮, 密霞, 孔媛芳, 杨怀霞.CN109896925 A, 2019)
[61] Hu Y.; Li J.; Chen W.; Hu W.CN 113683488 A, 2021 (in Chinese).
(胡玉林, 李精锐, 陈卫丰, 胡为民.CN 113683488 A, 2021)
[62] Acharyya S. S.; Ghosh S.; Siddiqui N.; Sivakumar Konathala, L. N.; Bal, R.RSC Adv. 2015, 5, 4838-4843.
[63] Liu X.; Ma X.; Ma Q.; Sun D.; Wei L.; Liu J.; Su J. CN 111606784 A, 2020 (in Chinese).
(刘显伟, 马心旺, 马青松, 孙东艳, 魏力璟, 刘娇, 苏建.CN 111606784 A, 2020)
[64] Shibahara F.; Kinoshita S.; Nozaki K. Org. Lett.2004, 6, 2437-2439.
[65] Holland H. L.; Morris T. A.; Nava P. J.; Zabic M. Tetrahedron1999, 55, 7441-7460.
[66] Minisci F.; Recupero F.; Cecchetto A.; Gambarotti C.; Punta C.; Paganelli, R. Org. Process Res. Dev.2004, 8, 163-168.
[67] Hirsch, R. Chem. Ber.1889, 22, 335-336.
[68] Wilds A. L.; Shunk C. H.; Hoffman, C. H. J. Am. Chem. Soc.1954, 76, 1733-1736.
[69] Vergura S.; Scafato P.; Belviso S.; Superchi S.Chem. Eur. J. 2019, 25, 5682-5690.
[70] Van Meter C. T.; Bianculli J. A.; Lowy, A. J. Am. Chem. Soc.1940, 62, 3146-3148.
[71] Jin E.; Fu S.; Hanayama H.; Addicoat M. A.; Wei W.; Chen Q.; Graf R.; Landfester K.; Bonn M.; Zhang K. A. I.; Wang H. I.; Müllen K.; Narita, A. Angew. Chem. Int. Ed.2022, 61, e202114059.
[72] Gennaiou K.; Petsi M.; Kakarikas B.; Iordanidis N.; Zografos, A. L. Adv. Synth. Catal.2022, 364, 3059-3065.
[73] Huang S.; Cui Y.; Wang B.; Liu F.-J.; Liu J.-Y.; Shao W.; Wang X.-Q.; Guo, Q. J. Med. Chem.2025, 68, 6656-6664.
[74] Yang L.; Yan Y.; Cao N.; Hao J.; Li G.; Zhang W.; Cao R.; Wang C.; Xiao J.; Xue D. Org. Lett.2022, 24, 9431-9435.
[75] Xu L.; Zhu J.; Shen X.; Chai J.; Shi L.; Wu B.; Li W.; Ma D.Angew. Chem. Int. Ed. 2024, 63, e202412552.
[76] Salazkin S. N.; Shaposhnikova V. V.; Donetskii K. I.; Gorshkov G. V.; Petrovskii P. V.; Komarova L. I.; Genina M. M.; Trachenko, A. S. Russ. Chem. Bull.2000, 49, 1093-1096.
[77] Hao L.; Auni A.; Ding G.; Li X.; Xu H.; Li T.; Zhang Q. RSC Adv.2021, 11, 25348-25353.
[78] Li Y.; Song M.; Luo S.; Ma C.; Li W.; Li S.; Chen Z.; Liu S.; Chen H.; Tian B. Org. Lett.2025, 27, 6485-6490.
[79] (a) Hwu J. R.; Wong F. F.; Huang J.-J.; Tsay, S.-C. J. Org. Chem.1997, 62, 4097-4104.
(b) Hwu J. R; Tsay, S.-C. J. Org. Chem.1990, 55, 5987-5991.
[80] Shirini F.; Khaligh N. G.; Akbari-Dadamahaleh, S.J. Mol. Catal. A-Chem. 2012, 365, 15-23.
[81] Prasad S. S.; Naidu B. R.; Hanafiah M. M.; Lakshmidevi J.; Marella R. K.; Lakkaboyana S. K.; Venkateswarlu K.Molecules 2021, 26, 5390.
[82] Prastaro A.; Ceci P.; Chiancone E.; Boffi A.; Fabrizi G.; Cacchi S.Tetrahedron Lett. 2010, 51, 2550-2552.
[83] Baig R. B. N.; Varma, R. S. Green Chem.2013, 15, 398-417.
[84] Minus M. B.; Moor S. R.; Pary F. F.; Nirmani L. P. T.; Chwatko M.; Okeke B.; Singleton J. E.; Nelson T. L.; Lynd N. A.; Anslyn, E. V. Org. Lett.2021, 23, 2873-2877.
[85] Appa R. M.; Lakshmidevi J.; Naidu B. R.; Venkateswarlu K. Mol. Catal.2021, 501, 111366.
[86] Contreras-Celedón C. A.; Mendoza-Rayo D.; Rincón-Medina J. A.; Chacón-García, L. Beilstein J. Org. Chem.2014, 10, 2821-2826.
[87] Kapdi A. R.; Dhangar G.; Serrano J. L.; De Haro J. A.; Lozano P.; Fairlamb, I. J. S. RSC Adv.2014, 4, 55305-55312.
[88] Di X.; Garnier T.; Clerc A.; Jung E.; Lherbet C.; Bénéteau V.; Pale P.; Chassaing S. Molecules2024, 29, 5552.
[89] Luque R.; Baruwati B.; Varma R. S. Green Chem. 2010, 12, 1540-1543.
[90] Jang W.; Byun H.; Kim J.-H. ChemCatChem2020, 12, 705-709.
[91] Lv Z.; Wang K.; Liu J.; Liu G.; Gan L.; Huang, Z. Chin. J. Chem.2025, 43, 2465-2470.
[92] Jin X.; Taniguchi K.; Yamaguchi K.; Mizuno N. Chem. Sci.2016, 7, 5371-5379.
[93] Jin X.; Taniguchi K.; Yamaguchi K.; Nozaki K.; Mizuno N.Chem. Commun. 2017, 53, 5267-5270.
[94] Zhong S.; Chen M.; Liu G.; Sun C.; Liu W.Appl. Organometal. Chem. 2017, 31, e3705.
[95] Singh P. P.; Gudup S.; Aruri H.; Singh U.; Ambala S.; Yadav M.; Sawant S. D.; Vishwakarma R. A.Org. Biomol. Chem. 2012, 10, 1587-1597.
[96] Fosshat S.; Fronczek F. R.; Chambers, M. B. Chem. Eur. J.2023, 29, e202300486.
[97] Riemer N.; Coswig C.; Shipman M.; Schmidt B. Synlett.2018, 29, 2427-2431.
Options
Outlines

/

〈 〉