综述与进展

4,4′-联苯二酚合成方法研究进展

  • 张怀远 ,
  • 王熙悦 ,
  • 刘荣 ,
  • 梁超荣 ,
  • 张其国 ,
  • 刘蓉蓉 ,
  • 陈子玮 ,
  • 梁茗钰
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  • a兰州石化职业技术大学 应用化学工程学院 兰州 730060;
    b甘肃省化工研究院有限责任公司 兰州 730020

收稿日期: 2026-06-21

  修回日期: 2026-08-16

  网络出版日期: 2026-09-16

基金资助

甘肃省教育厅科学研究项目(No. 2026CYZC-071)资助项目.

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).

摘要

4,4′-联苯二酚是合成先进聚合物、树脂及特种材料的关键基础原料,具有优异的热稳定性、化学耐受性和机械强度,可作为改性单体用于聚酯、聚氨酯、环氧树脂、液晶材料等领域,并在医药与农药合成中具有广泛应用. 该化合物结构中含有两个酚羟基,可发生取代、氧化等多种反应,衍生许多产物. 尽管4,4′-联苯二酚在多个行业中用途广泛,但目前高纯度(99.5%)产品仍全部依赖进口,合成面临重大挑战. 本文以合成4,4′-联苯二酚的原料为主线,系统梳理其多种合成路线,主要分为四类:以酚类化合物的氧化偶联、以联苯类化合物为骨架进行官能团转化、由4-羟基苯基衍生物构建联苯结构以及其他底物参与的方法,以期为高纯度4,4′-联苯二酚的合成研究提供参考.

本文引用格式

张怀远 , 王熙悦 , 刘荣 , 梁超荣 , 张其国 , 刘蓉蓉 , 陈子玮 , 梁茗钰 . 4,4′-联苯二酚合成方法研究进展[J]. 有机化学, 0 : 202606025 -202606025 . DOI: 10.6023/cjoc202606025

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.

参考文献

[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.
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