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化学进展 2022, Vol. 34 Issue (6): 1263-1274 DOI: 10.7536/PC211231 前一篇   后一篇

• 综述与评论 •

糠醛氧化合成糠酸

李兴龙, 傅尧*()   

  1. 中国科学技术大学 化学与材料科学学院 合肥 230026
  • 收稿日期:2021-12-27 修回日期:2022-03-17 出版日期:2022-04-01 发布日期:2022-04-01
  • 通讯作者: 傅尧
  • 基金资助:
    安徽省重大专项项目(18030701157); 安徽省自然科学基金项目(2008085QB63)
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Preparation of Furoic Acid by Oxidation of Furfural

Xinglong Li, Yao Fu()   

  1. School of Chemistry and Materials Science, University of Science and Technology of China,Hefei 230026, China
  • Received:2021-12-27 Revised:2022-03-17 Online:2022-04-01 Published:2022-04-01
  • Contact: Yao Fu
  • Supported by:
    Major Science and Technology Projects of Anhui Province(18030701157); Anhui Natural Science Foundation Project(2008085QB63)

糠酸作为糠醛的重要下游产品,在食品制造、材料制备、光学技术、药物合成中具有重要的应用,可用于合成防腐剂、增塑剂、热固性树脂、香料以及多种药物。目前,关于糠醛的制备以及催化氢化制备下游产物的综述报道相对较多,但是还没有系统地整理评述糠醛氧化合成糠酸的相关工作。本文综述了近年来以糠醛为主要原料制备糠酸的研究进展情况,讨论了不同催化体系及在不同氧源存在下对糠酸选择性的影响,重点突出了非均相催化剂在糠酸的工业化制备中的应用前景,对糠酸制备的未来发展方向进行了展望。

关键词： 生物质资源, 糠醛, 糠酸, 氧化, 非均相催化

As an important downstream product of furfural, furoic acid has important applications in food manufacturing, material preparation, optical technology and drug synthesis. It can be used to synthesize preservatives, plasticizers, thermosetting resins, spices and a variety of drugs. At present, there are many reviews on the preparation of furfural and the preparation of downstream compounds by hydrogenation. However, there is no systematic review on the oxidation of furfural to furoic acid. This paper reviews the progress in preparation of furoic acid from furfural in recent years. The effects of different catalytic systems and different oxygen sources on the selectivity of furoic acid are discussed. The application prospect of heterogeneous catalysts in the preparation of furoic acid is highlighted, and the future development direction of furoic acid preparation is prospected.

Contents

1 Introduction

2 Catalytic oxidation system

2.1 Homogeneous oxidation system

2.2 Heterogeneous oxidation system

2.3 Biological oxidation system

3 Conclusion and outlook

Key words: biomass resources, furfural, furoic acid, oxidation, heterogeneous catalysis
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图1 糠醛(左)和糠酸(右)相关论文近年来历年发表数量
Fig. 1 Number of publications on furfural (left) and furoic acid (right) annually in recent years. Source:Web of Science (keyword: furfural)
图2 糠醛转化制备多种重要的下游化合物
Fig. 2 Several important downstream compounds prepared by furfural
图3 糠酸到下游产品的转化
Fig. 3 Conversion of furoic acid to downstream products
表1 均相催化体系催化转化糠醛到糠酸反应汇总
Table 1 Summary of catalytic conversion of furfural to furoic acid by homogeneous catalytic system
Entry Catalyst Reaction conditions Furoic Acid Yield/% ref
1 [Cu(acac)2]/SIMes H2O, 50 ℃, 1 atm O2, 1 eq NaOH, 12 h 99 13
2 triazolium-NHC DABCO(50 mol%), O2, THF, r.t., 16 h 96 15
3 NaOH (1 eq), H2O, air, 80 ℃, 12 h 90 17
4 MeCN, TBD(1.2 eq), air, r.t. 86 17
5 CuCl 2 equiv of 70% t-BuOOH (in water) in MeCN, r.t., 3 h 91 18
6 CuBr2 2 equiv. t-BuOOH (water), MeCN, 1.5 h 92 19
7 Bi2O3 5 equiv. 70% t-BuOOH (water), EtOAc, 10 h 91 20
8 Mohr’s salt DMSO, 5 eq. 70% t-BuOOH, 80 ℃, 3.5 h 92 21
9 I2 NaOH (20 mol%), 4 equiv. t-BuOOH (water), H2O, 70 ℃, 10~16 h 77 22
10 PCC Solvent-free, r.t. 82 23
11 Sodium chlorite MeCN, 10 ℃-r.t., 3 h 90 24
12 H2O2; 60 ℃; CH3CN 76 25
13 CO2, DBU (20 mol%), THF, r.t., 10 min 65 26
14 H2O∶1,4-dioxane=50∶50, 95 ℃, 20 h 13.3 27
图4 [Cu(acac)2]/SIMes催化剂催化氧化醛到羧酸[13]
Fig. 4 Oxidation of aldehyde to acid by [Cu(acac)2]/SIMes catalysts[13]
图5 三唑钅翁-NHC催化剂催化氧化醛到羧酸[15]
Fig. 5 Oxidation of aldehyde to acid by Triazolium NHC catalyst[15]
图6 铱络合物催化剂催化氧化醛到羧酸[16]
Fig. 6 Oxidation of aldehyde to acid by iridium complex catalysts[16]
图7 NHC催化剂催化氧化醛到羧酸[17]
Fig. 7 Oxidation of aldehyde to acid by NHC catalysts[17]
图8 氯化亚铜-过氧叔丁醇氧化体系氧化醛到羧酸[18]
Fig. 8 Oxidation of aldehyde to acid by CuCl and t-BuOOH oxidation system[18]
图9 溴化铜-过氧叔丁醇催化体系氧化醛到羧酸[19]
Fig. 9 Oxidation of aldehydes to carboxylic acids by CuBr2 and t-BuOOH catalytic system[19]
图10 Mohr’s salt-过氧叔丁醇催化体系氧化醛到羧酸[21]
Fig. 10 Oxidation of aldehydes to carboxylic acids by Mohr’s salt and t-BuOOH catalytic system[21]
图11 碘-过氧叔丁醇催化体系氧化醇/醛到羧酸[22]
Fig. 11 Oxidation of alcohols or aldehydes to carboxylic acids by I2 and t-BuOOH catalytic system[22]
图12 PCC无溶剂条件下氧化醛到羧酸[23]
Fig. 12 Oxidation of aldehydes to carboxylic acids by PCC under solvent-free conditions[23]
图13 均相Ni催化剂氧化醛到酸和酯[25]
Fig. 13 Oxidation of aldehyde to acid and ester using Ni catalysts[25]
图14 二氧化碳介导的NHC催化醛到酸的反应及其机理图[26]
Fig. 14 Catalytic conversion of aldehyde to acid using carbon dioxide mediated NHC catalyst and its reaction mechanism[26]
图15 (六甲基苯)RuⅡ络合物催化剂氧化醛到羧酸[27]
Fig. 15 Catalytic conversion of aldehyde to acid using Hexamethyl-benzene-supported ruthenium complexes[27]
表2 非均相催化体系催化转化糠醛到糠酸反应汇总
Table 2 Summary of catalytic conversion of furfural to furoic acid by heterogeneous catalytic system
Entry Catalyst Reaction conditions Furoic Acid Yield/% ref
1 Au/ZTC methanol, 6 bar O2, 120 ℃, 6 h 90 28
2 AuNPs/TiO2 H2O, Na2CO3, 30 ℃, 8 h, UV/Uis 92/96 29
3 SiO2@Au@TiO2 FF : Au ratio=100, 2 h, 24 bar air 99 30
4 Co4HP2Mo15V3O62 [TEBSA][BF4], H2O2, r.t., 4 h 94 31
5 Co-N-C H2O, 120 ℃, 1 MPa O2,1h 96.7 32
6 SiO2-Co(acac)2
SiO2-Co(acac)2		 50 ℃, solvent-free, air, 5 h
70 ℃, H2O, air, 7.5 h		 85
180		 33
7 (NH4)4[CuMo6O18(OH)6] H2O, 50 ℃, O2 balloon, 0.1 eq Na2CO3, 8 h 99 34
8 Ag2O/CuO H2O, 70 ℃, 2 MPa O2, 1 h 99 35
9 CuO NaOH, H2O, 65 ℃, air, 25 min 91 36
10 FeIIIMo6 H2O, 50 ℃, 1 atm O2, 0.1 eq Na2CO3, 8 h 97 37
11 DBU (50 mol%), anhydrous Me-THF, air, r.t. 90 38
12 MnO2 H2O, NaHCO3, 1 MPa O2, 100 ℃, 24 h 95 39
13 Pd/C Methanol-H2O, NaBH4, KOH, air, r.t. 84 40
14 [Ce(NH4)2(NO3)6] (CAN) 1 eq. t-BuOOH (water), MeCN, r.t., 15 min 93 41
15 β- Cyclodextrin 50 ℃, H2O2, 1 h 97(conversion) 42
16 VO(acac)2-TiO2 (TSV) H2O2, MeCN, r.t., 4 h 86 43
17 MOF-TEMPO 1) 5 mol% catalyst, 20 mol% TBN, CH3CN, O2, 25 ℃, 2 h;2) the filtration of catalyst and additional stirring under O2 balloon at 80 ℃ for 10 h 80 44
图16 Co4HP2Mo15V3O62/H2O2催化体系转化糠醛到糠酸[31]
Fig. 16 Conversion of furfural to furoic acid by using Co4HP2Mo15V3O62/H2O2 catalytic system[31]
图17 铁(Ⅱ)酞菁与非均相三唑钅翁催化体系转化醛到羧酸[38]
Fig. 17 Conversion of aldehydes to acids catalyzed by iron (Ⅱ) phthalocyanine and heterogeneous triazolium catalytic system[38]
图18 二氧化锰催化转化糠醇或是糠醛到糠酸[39]
Fig. 18 Conversion of furfuryl alcohol or furfural to furoic acid by using MnO2 as catalysts[39]
图19 MOF-TEMPO催化氧化糠醇到糠酸[44]
Fig. 19 Conversion of furfuryl alcohol to furoic acid by using MOF-TEMPO as catalysts[44]
图20 NOX辅酶循环ALDHs催化醛的氧化[48]
Fig. 20 Oxidation of aldehydes by ALDHs using NOX for coenzyme recycling[48]
图21 GOase和ADHs双酶级联系统催化氧化醛到羧酸[50]
Fig. 21 A dual-enzyme cascade system of GOase and ADHs for catalytic oxidation of aldehydes to carboxylic acids[50]
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摘要

糠醛氧化合成糠酸