Research progress on the synthesis of 2,3,5-trimethyl-1,4-benzonquinone from one-step oxidation of 2,3,6-trimethylphenol

doi:10.16085/j.issn.1000-6613.2016.03.025

Abstract

Abstract: One-step oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzonquinone has many advantages over traditional sulfonated-oxidation process with higher yield,simpler and midler reaction condition and environment benign. Recent progresses on homogeneous and heterogeneous catalytic oxidation of 2,3,6-trimethylphenol were introduced and reviewed. The advantages and disadvantages of each method and route in catalytic activity,selectivity,product separation and catalyst recovery were discussed. The latest trends and development were analyzed and summarized. Micromechanism research on heterogeneous catalysis and industrialization exploration on catalyst cost and cyclical stability were considered as two potential research directions.

Key words: 2,3,6-trimethylphenol, 2,3,5-trimethyl-1,4-benzonquinone, catalysis, catalyst, oxidation

摘要： 2,3,6-三甲基苯酚一步氧化制备2,3,5-三甲基-1,4-苯醌相对于传统的磺化-氧化法具有产品收率高、过程简单、条件温和以及环境友好等特点。本文针对2,3,6-三甲基苯酚一步氧化制备2,3,5-三甲基-1,4-苯醌的均相催化氧化和非均相催化氧化工艺进行了综述,对两种工艺的发展过程及研究现状进行了评价及总结。详细讨论了不同方法和路线在催化活性、选择性以及产品分离和催化剂回收等方面的优缺点,简要分析并总结了2,3,6-三甲基苯酚一步氧化研究的发展规律和最新动态,展望了以非均相催化反应机制为重点的微观机理研究和以提高催化剂循环稳定性、降低制备成本为重点的工业化探索两个潜在的发展方向。

关键词: 2, 3, 6-三甲基苯酚, 2, 3, 5-三甲基-1, 4-苯醌, 催化, 催化剂, 氧化

CLC Number:

O625.42

YANG Chaoqun, ZHANG Xubin, SHEN Yu, LI Hang, WANG Fumin, CAI Wangfeng. Research progress on the synthesis of 2,3,5-trimethyl-1,4-benzonquinone from one-step oxidation of 2,3,6-trimethylphenol[J]. Chemical Industry and Engineering Progree, 2016, 35(03): 815-819.

杨超群, 张旭斌, 沈宇, 李航, 王富民, 蔡旺锋. 2,3,6-三甲基苯酚一步氧化制备2,3,5-三甲基-1,4-苯醌研究进展[J]. 化工进展, 2016, 35(03): 815-819.

References

[1] BONRATH W,EGGERSDORFER M,NETSCHER T. Catalysis in the industrial preparation of vitamins and nutraceuticals[J]. Catalysis Today,2007,121:45-57.

[2] BONRATH W,NETSCHER T. Catalytic processes in vitamins synthesis and production[J]. Applied Catalysis A:General,2005,280:55-73.

[3] 钱东,何厚群,王开毅. 直接氧化法合成2,3,5-三甲基氢醌[J]. 化学试剂,2002,24(4):231-232.

[4] MÖLLER K,WIENHÖFER G,WESTERHAUS F,et al. Oxidation of 1,2,4-trimethylbenzene (TMB),2,3,6-trimethylphenol (TMP) and 2-methylnaphthalene to 2,3,5-trimethylbenzoquinone (TMBQ) and menadione (vitamin K₃)[J]. Catalysis Today,2011,173(1):68-75.

[5] 白元胜,李子成,王立新,等. 2,3,5-三甲基氢醌的合成研究进展[J]. 合成化学,2014,22(3):423-428.

[6] HOFFMANN LA ROCHE. Verfahren zur herstellung von chinonen:German2221624(A1)[P]. 1972-11-30.

[7] DEGUSSA. Process for the preparation of 2,3,5-trimethyl-p-benzoquionne:US6262311(B1)[P]. 2001-07-17.

[8] BASF A G. Process for the preparation of 2,3,5-trimethyl-p- benzoquinone:EP0475272(A2)[P]. 1992-03-18.

[9] MITSUBISHI Gas Chemical Co. Process for the production of 2,3,5-trimethylbenzoquinone:EP0127888(A1)[P].1984-12-12.

[10] SHIMIZU M,WATANABE Y,ORITA H,et al. Synthesis of alkyl substituted p-benzoquinones from the corresponding phenols using molecular oxygen catalyzed by copper(Ⅱ) chloride-amine hydrochloride systems[J]. The Chemical Society of Japan,1992,65(6):1522-1526.

[11] SHIMZU M,WATANABE Y,ORITA H,et al. The oxidation of 2,4,6-trimethylphenol with molecular oxygen catalyzed by a copper(Ⅱ)-oxime or copper(Ⅱ)-amine system[J]. The Chemical Society of Japan,993,66(1):251-257.

[12] TAKEHIRA K,SHIMIZU M,WATANABE Y,et al. A novel synthesis of trimethyl-p-benzoquinone:Copper(Ⅱ)-hydroxylamine catalysed oxygenation of 2,3,6-trimethylphenoI with dioxygen[J]. J . Chem. Soc.,Chem. Commun.,1989,22:1705-1706.

[13] BODNAR Z,MALLAT T,BAIKER A. Oxidation of 2,3,6- trimethylphenol to trimethyl- 1,4-benzoquinone with catalytic amount of CuCl₂[J]. Journal of Molecular Catalysis A:Chemical,1996,110:55-63.

[14] BOON J A,LEVISKY J A,PFLUG L,et al. Friedel-Crafts reactions in ambient-temperature molten salts[J]. J. Org. Chem.,1986,51(4):480-483.

[15] DUPONT J,DE SOUZA R F,SUAREZ P A. Ionic liquid (molten salt) phase organometallic catalysis[J]. Chem. Rev.,2002,102(10):3667-3692.

[16] GORDON C M. New developments in catalysis using ionic liquids[J]. Applied Catalysis A:General,2001,222:101-117.

[17] SUN H J,HARMS K,SUNDERMEYER J. Aerobic oxidation of 2,3,6-trimethylphenol to trimethyl-1,4-benzoquinone with copper(II) chloride as catalyst in ionic liquid and structure of the active species[J]. J. Am. Chem. Soc.,2004,126:9550-9551.

[18] WANG C M,GUAN W,XIE P,et al. Effects of ionic liquids on the oxidation of 2,3,6-trimethylphenol to trimethyl-1,4-benzoquinone under atmospheric oxygen[J]. Catalysis Communications,2009,10(5):725-727.

[19] LI Y,ZHANG P,WU M,et al. An effective oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethylbenzoquinone using Fenton's reagent under mild conditions[J]. Chemical Engineering Journal,2009,146(2):270-274.

[20] ÇIMEN Y,TÜRK H. Oxidation of 2,3,6-trimethylphenol with potassium peroxymonosulfate catalyzed by iron and cobalt phthalocyanine tetrasulfonates in a methanol-water mixture[J]. Applied Catalysis A:General,2008,340(1):52-58.

[21] IVANCHIKOVA I D,MAKSIMCHUK N V,MAKSIMOVSKAYA R I,et al. Highly selective oxidation of alkylphenols to p-benzoquinones with aqueous hydrogen peroxide catalyzed by divanadium-substituted polyoxotungstates[J]. ACS Catalysis,2014,4(8):2706-2713.

[22] MENG X,SUN Z,LIN S,et al. Catalytic hydroxylation of 2,3,6-trimethylphenol with hydrogen peroxide over copper hydroxyphosphate [Cu₂(OH)PO₄][J]. Applied Catalysis A:General,2002,236(1/2):17-22.

[23] MASTRORILLI P,MUSCIO F,SURANNA G P,et al. Aerobic oxidation of substituted phenols catalysed by metal acetylacetonates in the presence of 3-methylbutanal[J]. Journal of Molecular Catalysis A,Chemical,2001,165(1):81-87.

[24] TAKAKI K,SHIMASAKI Y,SHISHIDO T,et al. Selective oxidation of phenols to hydroxybenzaldehydes and benzoquinones with dioxygen catalyzed by polymer-supported copper[J]. Bulletin of the Chemical Society of Japan,2002,75(2):311-317.

[25] FUJIBAYASHI S,NAKAYAMA K,HAMAMOTO M,et al. An efficient aerobic oxidation of various organic compounds catalyzed by mixed addenda heteropolyoxometalates containing molybdenum and vanadium[J]. Journal of Molecular Catalysis A:Chemical,1996,110(2):105-117.

[26] JANSEN R J J,VAN VELDHUIZEN H M,VAN BEKKUM H. Heteropoly anion on carbon:characterization and use in 2,3,6-trimethylphenol oxidation[J]. Journal of Molecular Catalysis A:Chemical,1996,107(1/2/3):241-246.

[27] KHOLDEEVA O A,GOLOVIN A V,MAKSIMOVSKAYA R I,et al. Oxidation of 2,3,6-trimethylphenol in the presence of molybdovanadophosphoric heteropoly acids[J]. Journal of Molecular Catalysis,1992,75(3):235-244.

[28] KHOLDEEVA O A,IVANCHIKOVA I D,GUIDOTTI M,et al. How to reach 100% selectivity in H₂O₂-based oxidation of 2,3,6-trimethylphenol to trimethyl-p-benzoquinone over Ti,Si- catalysts[J]. Catalysis Today,2009,141(3/4):330-336.

[29] SELVARAJ M. Highly active and green mesostructured titanosilicate catalysts synthesized for selective synthesis of benzoquinones[J]. Catalysis Science & Technology,2014,4(8):2674-2684.

[30] TUEL A,HUBERT-PFALZGRAF L G. Nanometric monodispersed titanium oxide particles on mesoporous silica:synthesis,characterization,and catalytic activity in oxidation reactions in the liquid phase[J]. Journal of Catalysis,2003,217(2):343-353.

[31] SOROKIN A B,TUEL A. Heterogeneous oxidation of aromatic compounds catalyzed by metallophthalocyanine functionalized silicas[J]. New Journal of Chemistry,1999,23(5):473-476.

[32] SOROKIN A B,MANGEMATIN S,PERGRALE C. Selective oxidation of aromatic compounds with dioxygen and peroxides catalyzed by phthalocyanine supported catalysts[J]. Journal of Molecular Catalysis A:Chemical,2002,182/183:267-281.

[33] NOTARI B. Titanium silicalites[J]. Catalysis Today,1993,18(2):163-172.

[34] TRUKHAN N N,ROMANNIKOV V N,PAUKSHTIS E A,et al. Oxidation of 2,3,6-trimethylphenol over Ti- and V-containing mesoporous mesophase catalysts:structure-activity/selectivity correlation[J]. Journal of Catalysis,2001,202(1):110-117.

[35] KHOLDEEVA O A,TRUKHAN N N,VANINA M P,et al. A new environmentally friendly method for the production of 2,3,5-trimethyl-p-benzoquinone[J]. Catalysis Today,2002,75(1/2/3/4):203-209.

[36] KHOLDEEVA O A,IVANCHIKOVA I D,GUIDOTTI M,et al. Highly efficient production of 2,3,5-trimethyl-1,4-benzoquinone using aqueous H₂O₂ and grafted Ti(Ⅳ)/SiO₂ catalyst[J]. Green Chemistry,2007,9(7):731-733.

[37] KHOLDEEVA O A,IVANCHIKOVA I D,GUIDOTTI M,et al. Highly selective oxidation of alkylphenols to benzoquinones with hydrogen peroxide over silica-supported titanium catalysts:titanium cluster site versus titanium single site[J]. Advanced Synthesis & Catalysis,2009,351(11/12):1877-1889.

[38] IVANCHIKOVA I D,KOVALEV M K,MEL'GUNOV M S,et al. User-friendly synthesis of highly selective and recyclable mesoporous titanium-silicate catalysts for the clean production of substituted p-benzoquinones[J]. Catal. Sci. Technol.,2014,4(1):200-207.

[39] KHOLDEEVA O A,MEL GUNOV M S,SHMAKOV A N,et al. A new mesoporous titanium-silicate Ti-MMM-2:a highly active and hydrothermally stable catalyst for H₂O₂-based selective oxidations[J]. Catalysis Today,2004,91/92:205-209.

[40] ZHAO D,YANG P,CHMELKA B F,et al. Multiphase assembly of mesoporous-macroporous membranes[J]. Chemistry of Materials,1999,11(5):1174-1178.

[41] INNOCENZI P,MALFATTI L,KIDCHOB T,et al. Order-disorder in self-assembled mesostructured silica films:a concepts review[J]. Chemistry of Materials,2009,21(13):2555-2564.

[42] SELVARAJ M,KANDASWAMY M,PARK D W,et al. Highly selective synthesis of vitamin K₃ over mesostructured titanium catalysts[J]. Catalysis Today,2010,158(3/4):377-384.

[43] TRUKHAN N N,KHOLDEEVA O A. Kinetics and mechanism of 2,3,6-trimethylphenol oxidation by hydrogen peroxide in the presence of TiO₂-SiO₂ aerogel[J]. Kinetics and Catalysis,2003,44(3):347-352.

[44] ZALOMAEVA O V,TRUKHAN N N,IVANCHIKOVA I D,et al. EPR study on the mechanism of H₂O₂-based oxidation of alkylphenols over titanium single-site catalysts[J]. Journal of Molecular Catalysis A:Chemical,2007,277(1/2):185-192.