交联菲罗啉负载铜催化剂用于合成三甲基苯醌

doi:10.11949/j.issn.0438-1157.20181322

摘要/Abstract

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2,3,6-三甲基苯酚（TMP）得到2,3,5-三甲基-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2,3,5-三甲基-1,4-苯醌的影响，得到最佳的工艺条件。当2,3,6-三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，2,3,5-三甲基-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。

关键词: 铜催化剂, 2,3,5-三甲基-1,4-苯醌, 氧化, 反应, 聚合物

Abstract:

Alkyl-substituted benzoquinones were versatile building blocks for a variety of biologically active compounds. The catalytic oxidation of 2,3,6-trimethylphenol (TMP) to 2,3,5-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 2,3,5-trimethyl-1,4-benzoquinone was obtained in 99% yield with the optimized reaction conditions. The optimized reaction conditions were achieved as 136 mg 2,3,6-trimethylphenol with 150 mg the Cu/PPhen-4 catalyst in 2 ml acetonitrile, under 0.5 MPa O₂ 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.

Key words: coper catalyst, 2,3,5-trimethyl-1,4-benzoquinone, oxidation, reaction, polymers

中图分类号:

TQ 466.5

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.

Wanwan GUO, Ruyue LI, Jun HUANG. 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.

图/表 12

图1 交联菲罗啉负载铜催化剂制备及其催化氧气氧化合成三甲基苯醌

Fig.1 Preparation of Cu/PPhen catalysts for catalyzed oxidation of TMP to TMQ

图2 交联聚菲罗啉PPhen及其负载铜催化剂Cu/PPhen-4的SEM图以及Cu/PPhen-4的元素映射图

Fig.2 SEM images of PPhen and Cu/PPhen-4，and EDS mapping of Cu/PPhen-4

图3 交联聚菲罗啉PPhen及其负载铜催化剂Cu/PPhen-4的氮气吸附脱附等温线及孔径分布

Fig.3 Nitrogen adsorption-desorption isotherm at 77 K and pore distribution of PPhen and Cu/PPhen-4

表1 交联聚菲罗啉PPhen及其负载铜催化剂Cu/PPhen-4的比表面积和孔容

Table 1 BET surface and pore volume of PPhen and Cu/PPhen-4

Sample	S _BET/(m²?g^-1)	V _S/(cm³?g^-1)
PPhen	381.3	0.6
Cu/PPhen-4	230.8	0.4

图4 交联聚菲罗啉PPhen及其负载铜催化剂Cu/PPhen-4的红外光谱图

Fig.4 FTIR spectra of PPhen and Cu/PPhen-4

图5 负载铜催化剂Cu/PPhen-4的XPS谱图及Cu 2p、N 1s的XPS谱图

Fig.5 XPS spectra of Cu/PPhen-4 and XPS spectra of Cu 2p and N 1s

表2 不同催化剂催化氧化TMP得到TMQ

Table 2 Oxidation of 2,3,6-trimethylphenol over different catalysts

Entry	Catalyst	TMP conversion^①/%	TMQ yield^②/%
1	none	trace	trace
2	PPhen	5	4
3	Cu/PPhen-1	46	45
4	Cu/PPhen-2	69	67
5	Cu/PPhen-4	100	99
6	Cu/PPhen-6	100	99
7	Cu/PPhen-10	100	98
8	Cu/C	40	38

图6 溶剂对Cu/PPhen-4催化氧气氧化TMP转化率和TMQ收率的影响

Fig.6 Effect of solvent on Cu/PPhen-4 catalyzed oxidation of TMP to TMQ

图7 氧气压力对Cu/PPhen-4催化氧化TMP获得TMQ的影响

Fig.7 Effect of O2 pressure on Cu/PPhen-4 catalyzed oxidation of TMP to TMQ

图8 反应温度对TMQ收率和TMP转化率的影响

Fig.8 Effect of reaction temperature on Cu/PPhen-4 catalyzed oxidation of TMP to TMQ

图9 反应时间对TMQ收率和TMP转化率的影响

Fig.9 Effect reaction time on Cu/PPhen-4 catalyzed oxidation of TMP to TMQ

图10 催化剂稳定性测试

Fig.10 Reusability of Cu/PPhen-4 catalyst for oxidation of TMP to TMQ

参考文献 41

1	Netscher T . Synthesis of vitamin E[J]. Vitamins and Hormones, 2007, 76: 155-202.
2	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.
3	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.
4	Bodnar Z , Mallat T , Baiker A . Oxidation of 2,3,6-trimethylphenol to trimethyl-1,4-benzoquinone with catalytic amount of CuCl₂ [J].J. Mol. Catal. A-Chem., 1996, 110(1): 55-63.
5	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.
6	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 CuCo₂O₄ [J]. J. Mol. Catal. A-Chem., 2006, 261(1): 73-78.
7	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.
8	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.
9	Neeli C K P , Ganjala V S P , Vakati V , et al . V₂O₅/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.
10	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.
11	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.
12	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.
13	Kholdeeva O A , Ivanchikova I D , Maksimchuk N V , et al . Environmentally benign oxidation of alkylphenols to p-benzoquinones: a comparative study of various Ti-containing catalysts[J]. Top Catal., 2014, 57(17-20): 1377-1384.
14	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.
15	Selvaraj M . Highly active and green mesostructured titanosilicate catalysts synthesized for selective synthesis of benzoquinones[J]. Catal. Sci. Technol., 2014, 4(8): 2674-2684.
16	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.
17	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.
18	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.
19	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.
20	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.
21	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.
22	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.
23	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.
24	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.
25	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.
26	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.
27	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.
28	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.
29	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.
30	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.
31	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.
32	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.
33	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.
34	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.
35	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.
36	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.
37	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.
38	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.
39	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.
40	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.
41	Mao F , Sui D J , Qi Z L , et al . Heterogeneous cobalt catalysts for reductive amination with H₂: general synthesis of secondary and tertiary amines[J]. RSC Adv., 2016, 6(96): 94068-94073.

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