Copper catalyst supported on cross-linked phenanthroline for oxidative synthesis of 2,3,5-trimethyl-1,4-benzoquinone

Wanwan GUO; Ruyue LI; Jun HUANG

doi:10.11949/j.issn.0438-1157.20181322

您当前的位置：

首页 >

文章列表页 >

Copper catalyst supported on cross-linked phenanthroline for oxidative synthesis of 2,3,5-trimethyl-1,4-benzoquinone

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Copper catalyst supported on cross-linked phenanthroline for oxidative synthesis of 2,3,5-trimethyl-1,4-benzoquinone
- CIESC Journal Vol. 70, Issue 3, Pages: 929-936(2019)
- 作者机构：
  
  南京工业大学化工学院，江苏南京 211816
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20181322
  CLC： TQ 466.5
- Received：12 November 2018，
  
  Revised：2018-12-05，
  
  Online First：24 July 2026，
  
  Published：05 March 2019
- 稿件说明：
移动端阅览
郭婉婉, 李如月, 黄军. 交联菲罗啉负载铜催化剂用于合成三甲基苯醌[J]. 化工学报, 2019, 70(3): 929-936

GUO Wanwan, LI Ruyue, HUANG Jun. Copper catalyst supported on cross-linked phenanthroline for oxidative synthesis of 2,3,5-trimethyl-1,4-benzoquinone[J]. CIESC Journal, 2019, 70(3): 929-936
郭婉婉, 李如月, 黄军. 交联菲罗啉负载铜催化剂用于合成三甲基苯醌[J]. 化工学报, 2019, 70(3): 929-936 DOI： 10.11949/j.issn.0438-1157.20181322.

GUO Wanwan, LI Ruyue, HUANG Jun. Copper catalyst supported on cross-linked phenanthroline for oxidative synthesis of 2,3,5-trimethyl-1,4-benzoquinone[J]. CIESC Journal, 2019, 70(3): 929-936 DOI： 10.11949/j.issn.0438-1157.20181322.

摘要

烷基取代的苯醌可用作多种生物活性化合物的功能结构单元。提出了一种在温和条件下，用氧气氧化2

6-三甲基苯酚（TMP）得到2

5-三甲基-1

4-苯醌（TMQ，维生素E前体）的方法。利用Friedel-Crafts烷基化反应，成功制备了一种基于1

10-菲罗啉的交联多孔聚合物负载铜催化剂Cu/PPhen。采用氮气吸附脱附、SEM、FTIR和XPS对催化剂Cu/PPhen-4进行了一系列的表征，获得了催化剂的基本结构特征。并考察了催化剂的加入量、溶剂、氧气压力、反应温度以及反应时间等因素对Cu/PPhen-4催化氧化制备2

5-三甲基-1

4-苯醌的影响，得到最佳的工艺条件。当2

6-三甲基苯酚的加入量为136 mg时，催化剂量为150 mg，乙腈量为2 ml，0.5 MPa的氧气，40℃下反应4 h，2

5-三甲基-1

4-苯醌的收率可以达到99%。催化剂Cu/PPhen-4具有较好的稳定性，可以回收至少五次，活性几乎没有下降。

Abstract

Alkyl-substituted benzoquinones were versatile building blocks for a variety of biologically active compounds. The catalytic oxidation of 2

6-trimethylphenol (TMP) to 2

5-trimethyl-1

4-benzoquinone (TMQ

vitamin E precursor) with oxygen gas was proposed under mild conditions. The cross-linked porous polymer (PPhen) was synthesized by Friedel-Crafts alkylation of 1

10-phenanthroline

and the related Cu catalysts (Cu/PPhen) were prepared. The prepared Cu/PPhen catalysts were characterized by nitrogen adsorption and desorption isotherms

scanning electron microscope (SEM)

Fourier transform infrared spectroscopy (FTIR)

and X-ray photoelectron spectroscopy (XPS) .The basic structure of the Cu/PPhen catalysts were obtained. Reaction conditions

such as catalyst loading

solvent

oxygen pressure

reaction temperature and reaction time were studied

and 2

5-trimethyl-1

4-benzoquinone was obtained in 99% yield with the optimized reaction conditions. The optimized reaction conditions were achieved as 136 mg 2

6-trimethylphenol with 150 mg the Cu/PPhen-4 catalyst in 2 ml acetonitrile

under 0.5 MPa O

at 40℃ for 4 h. The Cu/PPhen-4 catalyst has good stability and can be recovered at least five times with almost no decrease in activity.

关键词

Keywords

references

Netscher T . Synthesis of vitamin E [J ] . Vitamins and Hormones , 2007 , 76 : 155 - 202 .

Finsterer J . Stroke-like episodes in coenzyme-Q deficiency may respond to NO-precursors and non-mitochondrion-toxic antiepileptic drugs [J ] . Molecular Genetics and Metabolism Reports , 2018 , 17 : 42 .

Detering T , Linke D , Gounel S , et al . Laccase-catalysed cleavage of malvidin-3-O-galactoside to 2,6-dimethoxy-1,4- benzo- quinone and a coumarin galactoside [J ] . Mycol. Prog ., 2018 , 17 ( 6 ): 681 - 690 .

Bodnar Z , Mallat T , Baiker A . Oxidation of 2,3,6-trimethylphenol to trimethyl-1,4-benzoquinone with catalytic amount of CuCl 2 [J ] .J. Mol . Catal. A-Chem ., 1996 , 110 ( 1 ): 55 - 63 .

Saux C . Greener method to obtain a key intermediate of vitamin E over Cu-ZSM-5 [J ] . Ind. Eng. Chem. Res ., 2014 , 53 ( 28 ): 11276-11283 .

Li Y , Liu W , Wu M Z , et al . Oxidation of 2,3,5-trimethylphenol to 2,3,5-trimethylbenzoquinone with aqueous hydrogen peroxide in the presence of spinel CuCo 2 O 4 [J ] . J. Mol . Catal. A-Chem ., 2006 , 261 ( 1 ): 73 - 78 .

Chattopadhyay T , Kogiso M , Aoyagi M , et al . Single bilayered organic nanotubes: anchors for production of a reusable catalyst with nickel ions [J ] . Green Chem ., 2011 , 13 ( 5 ): 1138 - 1140 .

Evtushok V Y , Suboch A N , Podyacheva O Y . Highly efficient catalysts based on divanadium-substituted polyoxometalate and N‑doped carbon nanotubes for selective oxidation of alkylphenols [J ] . ACS Catal ., 2018 , 8 ( 2 ): 1297 - 1307 .

Neeli C K P , Ganjala V S P , Vakati V , et al . V 2 O 5 /SBA-15 nanocatalysts for the selective synthesis of 2,3,5-trimethyl-1,4-benzoquinone at room temperature [J ] . New J.Chem ., 2006 , 40 ( 1 ): 679 - 686 .

Ivanchikova I D , Maksimchuk N V , Maksimovskaya R I . Highly selective oxidation of alkylphenols to p ‑benzoquinones with aqueous hydrogen peroxide catalyzed by divanadium-substituted polyoxotungstates [J ] . ACS Catal ., 2014 , 4 ( 8 ): 2706 - 2713 .

Fallah A H , Endud S , Alizadeh A , et al . Metalloporphyrin/dendrimer-decorated MCM-41 biomimetic hybrid catalysts: high stability combined with facile catalyst recyclability [J ] . Journal of Porous Materials , 2018 , 25 ( 6 ): 1813 - 1823 .

Li Y , Zhang P , Wu M Z , et al . An effective oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethylbenzoquinone using Fenton s reagent under mild conditions [J ] . Chem. Eng. J ., 2009 , 146 ( 2 ): 270 - 274 .

Kholdeeva O A , Ivanchikova I D , Maksimchuk N V , et al . Environmentally benign oxidation of alkylphenols to p -benzoquinones: a compa rative study of various Ti-containing catalysts [J ] . Top Catal ., 2014 , 57 ( 17-20 ): 1377 - 1384 .

Lin T H , Chen C C , Jang L Y , et al . Preparation and catalytic properties of mesoporous titanosilicate of cubic Pm3n structure [J ] . Micropor. Mesopor. Mat ., 2014 , 198 : 194 - 202 .

Selvaraj M . Highly active and green mesostructured titanosilicate catalysts synthesized for selective synthesis of benzoquinones [J ] . Catal. Sci. Technol ., 2014 , 4 ( 8 ): 2674 - 2684 .

Koreniuk A , Maresz K , Odrozek K , et al . Titania-silica monolithic multichannel microreactors. Proof of concept and fabrication/structure/catalytic properties in the oxidation of 2,3,6-trimethylphenol [J ] . Micropor. Mesopor. Mat ., 2016 , 229 : 98 - 105 .

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 .

Torbina V V , Vodyankin A A , Ivanchikova I D , et al . Support pretreatment effect on the catalytic properties and reusability of silica-supported titania catalysts in 2,3,6-trimethylphenol oxidation with hydrogen peroxide [J ] . Kinet. Catal ., 2015 , 56 ( 3 ): 370 - 376 .

Pirovano C , Guidotti M , Santo V D , et al . Use of titanium-containing silica catalysts prepared by rapid and straightforward method in selective oxidations [J ] . Catal. Today , 2012 , 197 ( 1 ): 170 - 177 .

Gao X , An J G , Gu J L , et al . A green template-assisted synthesis of hierarchical TS-1 with excellent catalytic activity and recyclability for the oxidation of 2,3,6-trimethylphenol [J ] . Micropor. Mesopor. Mat ., 2017 , 239 : 381 - 389 .

Podgorsek A , Zupan M , Iskra J . Oxidative halogenation with “green” oxidants: oxygen and hydrogen peroxide [J ] . Angew. Chem. Int. Ed ., 2009 , 48 ( 45 ): 8424 - 8450 .

Sheldon R A , Kochi J K . Metal-catalyzed oxidation of organic compounds in the liquid phase: a mechanistic approach [J ] . Adv.Catal ., 1976 , 25 : 272 - 413 .

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 ( 31 ): 9550 - 9551 .

Sun H J , Li X Y , Sundermeyer J . Aerobic oxidation of phenol to quinone with copper chloride as catalyst in ionic liquid [J ] . J. Mol . Catal. A-Chem ., 2005 , 240 ( 1 / 2 ): 119 - 122 .

Li B , Guan Z H , Wang W , et al . Highly dispersed Pd catalyst locked in knitting aryl network polymers for Suzuki-Miyaura coupling reactions of aryl chlorides in aqueous media [J ] . Adv. Mater ., 2012 , 24 ( 25 ): 3390 - 3395 .

Wang X B , Min S X , Das S K , et al . Spatially isolated palladium in porous organic polymers by direct knitting for versatile organic transformations [J ] . J. Catal ., 2017 , 355 : 101 - 109 .

Li Y , Mao F , Chen T , et al . In situ trapped and immobilized palladium nanoparticles as active and clean catalysts for Suzuki-Miyaura reaction [J ] . Adv. Synth. Catal ., 2015 , 357 ( 13 ): 2827 - 2832 .

Geng L F , Li Y , Qi Z L , et al . Highly efficient palladium catalysts supported on nitrogen contained polymers for Suzuki-Miyaura reaction [J ] . Catal. Commun ., 2016 , 82 : 24 - 28 .

Chen T , Mao F , Qi Z L , et al . Immobilized palladium nanoparticles within polymers as active catalysts for Suzuki-Miyaura reaction [J ] . RSC Adv ., 2016 , 6 ( 20 ): 16899-16903 .

Fan H P , Qi Z L , Sui D J , et al . Palladium nanoparticles in cross-linked polyaniline as highly efficient catalysts for Suzuki-Miyaura reactions [J ] . Chinese Journal of Catalysis , 2017 , 38 ( 3 ): 589 - 596 .

Yu Y P , Hu T J , Chen X R , et al . Pd nanoparticles on a porous ionic copolymer: a highly active and recyclable catalyst for Suzuki-Miyaura reaction under air in water [J ] . Chem. Commun ., 2011 , 47 ( 12 ): 3592 - 3594 .

Marko I E , Giles P R , Tsukazaki M , et al . Copper-catalyzed oxidation of alcohols to aldehydes and ketones: an efficient, aerobic alternative [J ] . Science , 1996 , 274 ( 5295 ): 2044 - 2046 .

Ten B G J , Arends I W C E , Sheldon R A . Green, catalytic oxidation of alcohols in water [J ] . Science , 2000 , 287 ( 5458 ): 1636 - 1639 .

黄军 , 祁正亮 . 钴催化剂及其制备方法和在催化合成2,3,5-三甲基苯醌中的应用: 107185571A [P ] . 2017-09-22 .

Huang J , Qi Z L . The preparation method of cobalt catalyst and its application in catalytic synthesis of 2,3,5-trimethylphenylhy-drazine: 107185571A [P ] . 2017-09-22 .

黄军 , 祁正亮 . 一种铼催化剂及其催化合成2-甲基-1,4-萘醌的方法: 106622325A [P ] . 2017-05-10 .

Huang J , Qi Z L . Rhenium catalyst and its catalytic synthesis of 2-methyl-1,4-naphthoquinone: 106622325A [P ] . 2017-05-10 .

黄军 , 李冰 . 一种钒催化剂及其催化合成2,3,5-三甲基苯醌的方法: 104399507A [P ] . 2015-03-11 .

Huang J , Li B . Vanadium catalyst and its catalytic synthesis of 2,3,5-trimethylphenylhydrazine: 104399507A [P ] . 2015-03-11 .

黄军 , 周志成 . 一种氧化制备2,3,5-三甲基苯醌的方法: 105693490A [P ] . 2016-06-22 .

Huang J , Zhou Z C . The method for preparing 2,3,5-trimethyl-phenylhydrazine by oxidation: 105693490A [P ] . 2016-06-22 .

Xu S J , Song K P , Li T , et al . Palladium catalyst coordinated in knitting N-heterocyclic carbene porous polymers for efficient Suzuki-Miyaura coupling reactions [J ] . J. Mater . Chem. A ., 2015 , 3 ( 3 ): 1272 - 1278 .

Zheng T , Wang T , Ma R Q , et al . Influences of isolated fractions of natural organic matter on adsorption of Cu(Ⅱ) by titanate nanotubes [J ] . Sci. Total. Environ ., 2019 , 650 ( 1 ): 1412 - 1418 .

Ma Y X , Shao W J , Sun W , et al . One-step fabrication of beta-cyclodextrin modified magnetic graphene oxide nanohybrids for adsorption of Pb(Ⅱ), Cu(Ⅱ) and methylene blue in aqueous solutions [J ] . Appl. Surf. Sci ., 2018 , 459 : 544 - 553 .

Mao F , Sui D J , Qi Z L , et al . Heterogeneous cobalt catalysts for reductive amination with H 2 : general synthesis of secondary and tertiary amines [J ] . RSC Adv ., 2016 , 6 ( 96 ): 94068-94073 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Synthesis, structure and properties of high refrective index polythiourethane

Progress in research of selective oxidation of low carbon polyols over nano-Au catalysts with precise electronic effect regulation

Study on boiling characteristics of liquid crystal elastomer surfaces with thermally adaptive wettability

Numerical study on damage behavior of rubber O-ring seals under hydrogen-friction coupling effects

Research progress of ionic liquids in separation of aromatics/alkanes and olefins/alkanes

Related Author

YING Xin

DU Miao

PAN Pengju

SHAN Guorong

ZHAO Mingyue

MENG Fanyu

YAN Hao

FENG Xiang

Related Institution

Polytechnic Institute, Zhejiang University

Institute of Zhejiang University-Quzhou

State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University

Department of Polymer Science and Engineering, Zhejiang University

State Key Laboratory of Heave Oil Processing, China University of Petroleum (East China)

⁰