In-situ oxidation of 5-hydroxymethylfurfural to 5-formylfuran-2-carboxylic acid catalyzed by iron, manganese, copper and salicylic amantadine Schiff base ligands
-
摘要: 本研究将铁、锰、铜和金刚烷胺缩水杨醛衍生的席夫碱配体组成的原位催化剂用于催化5-羟甲基糠醛(5-Hydroxymethylfurfural,简称HMF)选择性氧化制备5-甲酰基呋喃-2-羧酸(5-formyl-2-furancarboxylic acid,简称FFCA)。通过核磁共振(NMR)、红外(FT-IR)和单晶衍射对配体和配合物进行了表征,并对氧化反应时间、反应温度、MnCl2·4H2O与配体物质的量比、氧化剂和催化剂用量等反应条件进行优化,在最优化条件下,HMF转化率为100%,并且可以获得收率为52.1%的FFCA。根据反应结果对Mn金属配合物催化的HMF氧化反应过程进行了分析。
-
关键词:
- 5-羟甲基糠醛 /
- 氧化 /
- 席夫碱 /
- 原位催化 /
- 5-甲酰基呋喃-2-羧酸
Abstract: To synthesize simple and efficient catalysts and their application in catalytic conversion of biomass platform compounds to prepare high value-added chemicals has always been the focus of researchers. In this paper, a catalyst composed of iron, manganese, copper and Schiff base ligand derived from amantadine salicylaldehyde was in-situ constructed to catalyze the selective oxidation of 5-hydroxymethylfurfural (HMF) to prepare 5-formyl-2-furancarboxylic acid (FFCA). The ligands and complexes were characterized by nuclear magnetic resonance (NMR), infrared spectroscopy (IR) and single crystal diffraction, and the reaction conditions such as oxidation reaction time, reaction temperature, molar ratio of MnCl2·4H2O to ligand, oxidant and catalyst dosage, etc, were optimized. Under the optimized conditions, 100% conversion of HMF and the FFCA with a yield of 52.1% can be obtained. Finally, on the basis of the reaction results, the HMF oxidation reaction process catalyzed by Mn metal complexes was analyzed.-
Key words:
- 5-hydroxymethylfurfural /
- oxidation /
- Schiff base /
- in-situ catalysis /
- 5-formylfuran-2-carboxylic acid
-
图 2 水杨醛缩金刚烷胺席夫碱配体的合成路径
Figure 2 Synthetic route of salicylaldehyde amantadine Schiff base ligand
Yellow solid:1H NMR (400 MHz, CDCl3): 14.51 (s, 1H), 8.32 (s, 1H), 7.25−7.29 (m, 2H), 6.93 (d, J= 8.0 Hz, 1H), 6.83 (t, J = 8.0 Hz, 1H), 2.18 (s, 3H), 1.84 (d, J=4.0 Hz, 6H),1.78−1.68 (m, 6H); 13C NMR (400 MHZ, CDCl3): 162.4, 159.2, 132.0, 131.3, 118.9, 118.0, 117.4, 57.1, 43.0, 36.3, 29.4; FT-IR (KBr, cm−1): 1613 (w), 1210 (m)
表 1 配合物3的单晶数据
Table 1 Single crystal data for complex 3
Bond precision C−C = 0.0065 Å Wavelength=0.71073 Cell a=24.6241(15) b=10.3788(7) c=12.5427(8) alpha=90 beta=118.324(2) gamma=90 Temperature 296 K calculated reported Volume 2821.8(3) 2821.7(3) Space group C2/c C2/c Hall group −C2yc −C2yc Moiety formula C34H40CuN2O2 Sum formula C34H40CuN2O2 C34H40CuN2O2 Mr 572.23 572.22 Dx/(g·cm−3) 1.347 1.347 Z 4 4 Mu/mm−1 0.808 0.808 F000 1212.0 1212.0 F000' 1213.65 h, k, lmax 29, 12, 14 29, 12, 14 Nref 2509 2503 Tmin, tmax 0.851 0.872 Tmin' 0.851 Correction method= not given
Data completeness= 0.998, theta(max)= 25.058
R(reflections)= 0.0593(1778), wR2(reflections)= 0.1612(2503)
S = 1.008, Npar=177表 2 不同种类催化剂对HMF氧化反应催化性能比较
Table 2 Comparison of different types of catalysts for oxidation of HMF
Entry Catalyst Conversion/% HMFCA/% DFF/% FFCA/% FDCA/% 1 − 27.1 0 2.3 2.9 0 2 L 9.3 0 0.9 1.7 0 3 MnCl2·4H2O 36.1 0 9.1 15.2 0 4 FeCl3 19.8 3.3 2.0 3.4 0 5 CuCl2·2H2O 14.8 0 2.3 7.6 0 6 Complex 1 80.1 0 15.2 20.0 0 MnCl2·4H2O+L 76.3 0 16.3 21.7 0 7 Complex 2 36.3 14.5 7.8 3.9 0 FeCl3+ L 33.7 13.0 6.6 2.7 0 8 Complex 3 52.8 0 12.2 9.1 0 CuCl2·2H2O + L 47.3 0 10.2 8.2 0 Reaction condition:1 mmol HMF, 5% Cat., 0.05 mmol metal, 0.1 mmol ligand, 3 mmol TBHP, 4 mL DMSO, 12 h, 70 ℃ 表 3 催化剂用量对HMF氧化的影响
Table 3 Influence of dosage of catalyst on HMF oxidation
Catalyst/% Conversion/% DFF/% FFCA/% FDCA/% 1 92.7 8.2 21.5 0 3 100 14.3 48.6 10.5 5 100 10.2 36.4 6.1 7 100 10.2 29.3 5.7 10 100 10.2 29.3 5.7 Reaction condition:1 mmol HMF, 3 mmol TBHP, 4 mL DMSO, 18 h, 90 ℃ 表 4 不同溶剂对HMF氧化的影响
Table 4 Influence of different solvents on HMF oxidation
Entry Solvent HMF/% HMFCA/% DFF/% FFCA/% FDCA/% 1 DMF 76.4 7.7 8.3 7.5 0 2 CH3CN 100 0 7.8 21.7 0 3 CH3OH 60.6 0 8.8 0 0 4 H2O 37.2 0 8.8 0 0 5 DMSO 100 0 16.3 52.1 13.2 Reaction condition:1 mmol HMF, 3% Cat., 3 mmol TBHP, 4 mL solvent, 18 h, 90 ℃ 表 5 不同氧化剂对HMF氧化反应的影响
Table 5 Influence of different oxidant on HMF oxidation
Oxidant Conversion/% DFF/% FFCA/% FDCA/% O2 53.5 2.6 4.5 9.7 H2O2 76.0 3.2 4.4 2.5 TBHP 100 16.3 52.1 13.2 Reaction condition:1 mmol HMF, 0.03 mmol MnCl2·4H2O, 0.03 mmol ligand, 3 mmol oxidation, 4 mL DMSO, 18 h, 90 ℃ 表 6 不同底物氧化反应的比较
Table 6 Comparison of different substrate oxidation reactions
Substrate HMFCA/% DFF/% FFCA/% FDCA/% HMF 0 16.3 52.1 13.2 DFF 0 0 67.2 17.9 FFCA 0 0 82.3 10.6 Reaction condition:1 mmol substrate, 0.03 mmol MnCl2·4H2O, 0.03 mmol ligand, 3 mmol oxidation, 4 mL DMSO, 18 h, 90 ℃ 表 7 用各种催化剂将HMF氧化为FFCA
Table 7 Oxidation of HMF to FFCA with various catalysts
Catalyst type Conversion/% FFCA/% Reaction conditions Ref. Na3H6FeMo6O24·5H2O 82 75 environment :alkalinity
oxidant:30 mL/min O2
time:8 h
temperature:100 ℃[14] AuNPs-sPSB 99 82 environment:alkalinity
oxidant:2.5−3.5 MPa O2
time:6 h
temperature:110 ℃[26] g-C3N4/NaNbO3 35.8 31.3 environment:alkalinity
oxidant:10 mL/min O2
time:6 h
300 W xenon lamp, λ>400 nm[15] MnzFeyOx 83 37.7 environment:alkalinity
oxidant:3.0 MPa O2
time:1.5 h
temperature:140 ℃[16] MnCl2·4H2O+L5 >98 52.1 environment:non alkaline
oxidant:1.0 mL/min
time:18 h
temperature:90 ℃this work -
[1] MURPHY J D, BROWNE J, ALLEN E, GALLAGHER C. The resource of biomethane, produced via biological, thermal and electrical routes, as a transport biofuel[J]. Renewable Energy,2013,55(1):474−479. [2] LICHTENTHALER F W, PETER S. Carbohydrates as green raw materials for the chemical industry[J]. Comptes Rendus Chimie,2004,7(2):65−90. doi: 10.1016/j.crci.2004.02.002 [3] SIANKEVICH S, SAVOGLIDIS G, FEI Z. A novel platinum nanocatalyst for the oxidation of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid under mild conditions[J]. J Catal,2014,315(6):67−74. [4] CORMA A, IBORRA S, VELTY A. Chemical routes for the transformation of biomass into chemicals[J]. Chem Rev,2007,107(6):2411−2502. doi: 10.1021/cr050989d [5] ROMÁN-LESHKOV Y, CHHEDA J N, DUMESIC J A. Phase modifiers promote efficient production of hydroxymethylfural from fructose[J]. Dumesic Sci,2006,312(5782):1933−1937. doi: 10.1126/science.1126337 [6] ZHAO H, HOLLADAY J E, BROWN H, ZHANG Z C. Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural[J]. Science,2007,316(5831):1597−1600. doi: 10.1126/science.1141199 [7] SUN Z, CHENG M X, LI Z J, TIAN J, WANG X H. One pot production of 5-hydroxymethylfurfural with high yield from cellulose by a Brønsted-Lewis- surfactant-combined heteropolyacid catalyst[J]. Chem Commun,2011,47(7):2176−2178. doi: 10.1039/c0cc04444j [8] STÅHLBERG T, FU W, WOODLEY J M, RIISAGER A. Synthesis of 5-(hydroxymethyl) furfural in ionic liquids: Paving the way to renewable chemicals[J]. ChemSusChem,2011,4(4):451−458. doi: 10.1002/cssc.201000374 [9] LAN J, LIN J, CHEN Z, YIN G. Transformation of 5-hydroxymethylfurfural (HMF) to maleic anhydride by aerobic oxidation with heteropolyacid catalysts[J]. ACS Catal,2015,5(4):2035−2041. doi: 10.1021/cs501776n [10] PAL P, SARAVANAMURUGAN S. Recent advances in the development of 5-hydroxymethylfurfural oxidation with base (nonprecious)-metal-containing catalysts[J]. ChemSusChem,2018,12(1):145−163. [11] ZHANG Z, DENG K. Recent advances in the catalytic synthesis of 2, 5-furandicarboxylic acid and its derivatives[J]. ACS Catal,2015,5(11):6529−6544. doi: 10.1021/acscatal.5b01491 [12] ZHANG C, CHANG X, ZHU L, XING Q, YOU S, QI W, SU R, HE Z. Highly efficient and selective production of FFCA from CotA-TJ102 laccase-catalyzed oxidation of 5-HMF[J]. Int J Biol Macromol,2019,128(1):132−139. [13] GANDINI A, SILVESTRE A J D, NETO C P, SOUSA A F, GOMES M, The furan counterpart of poly(ethylene terephthalate): An alternative material based on renewable resources[J] J Polym Sci Pol Chem, 2009, 47 (1) 295−298. [14] XU J J, ZHU Z G, YUAN Z L, SUN T, ZHAO Y C, REN W Z, ZHANG Z H, LÜ H Y. Selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furancar- boxylic acid over a Fe-Anderson type catalyst[J]. J Taiwan Inst Chem E,2019,104:8−15. [15] ZHU Y, ZHANG Y, CHENG L, ISMAEL M, FENG Z, WU Y. Novel application of g-C3N4/NaNbO3 composite for photocatalytic selective oxidation of biomass-derived HMF to FFCA under visible light irradiation[J]. Adv Powder Technol,2020,31(3):1148−1159. doi: 10.1016/j.apt.2019.12.040 [16] PAL P, KUMAR S, DEVI M M, SARAVANAMURUGAN S. Oxidation of 5-hydroxymethylfurfural to 5-formyl furan-2-carboxylic acid by non-precious transition metal oxide-based catalyst[J]. J Supercrit Fluids,2020,160(1):104−812. [17] VENTURA M, ARESTA M, DIBENEDETTO A. Selective aerobic oxidation of 5-(hydroxymethyl) furfural to 5-formyl-2-furancarboxylic acid in water[J]. ChemSusChem,2016,9(10):1096−1100. doi: 10.1002/cssc.201600060 [18] VENTURA M, LOBEFARO F, GIGLIO E, DISTASO M, NOCITO F, DIBENEDETTO A. Selective aerobic oxidation o 5-hydroxymethylfurfural to 2, 5-diformylfuran or 2-formyl-5-furancarboxylic acid in water by using MgO·CeO2 mixed oxides as catalysts[J]. ChemSusChem,2018,11(8):1305−1315. doi: 10.1002/cssc.201800334 [19] WANG H B. Synthesis, characterization and antibacterial activity of Schiff base containing adamantyl and Its Zinc complex[D]. Liaoning: Liaoning University, 2012. [20] JIN X D, WANG W C, FENG X X, BU L C, TONG J, ZHANG P, REN J K, ZHAO B X. Synthesis, characterization, crystal structure, and electrochemical property of copper(II) complexes with Schiff bases derived from 5-halogenated salicylaldehyde and amantadine[J]. J Coord Chem,2017,43(11):787−794. doi: 10.1134/S1070328417110033 [21] SHELDRICK G M. SHELXT-integrated space-group and cry-synthesis determination[J]. Acta Crystallogr A,2015,71(1):3−8. [22] JIN X D, KOU L, LIANG H M, TONG J, ZHANG P, HAN G C, REN J K, ZHAO B X. Syntheses and crystal structures of three copper(II) complexes with bulky Schiff bases derived from rimantadine[J]. J Coord Chem,2016,69(22):3309−3320. doi: 10.1080/00958972.2016.1228910 [23] KIM M, SU Y Q, FUKUOKA A, HENSEN E J M, NAKAJIMA K. Aerobic oxidation of 5-(hydroxymethyl) furfural cyclic acetal enables selective furan-2, 5-dicarboxylic acid formation with CeO2-supported gold catalyst[J]. Angew Chem Int Ed,2018,57(27):8235−8239. doi: 10.1002/anie.201805457 [24] RAO V K, PETER S. Oxidation of biomass derived 5-hydroxymethylfurfural using heterogeneous and electrochemical catalysis[J]. Catal Today, 2012, 195(1): 144−154. [25] REN Y S, LIU B, ZHANG Z H, LIN J T. Silver-exchanged heteropolyacid catalyst (Ag1H2PW): An efficient heterogeneous catalyst for the synthesis of 5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose[J]. J Ind Eng Chem,2015,21(25):1127−1131. [26] JU E G, DONG K, CHEN Z W, LIU Z, LIU C Q, HUANG Y Y, WANG Z Z, PU F, REN J S, QU X G. Copper(ii) -graphitic carbon nitride triggered synergy: Improved ros generation and reduced glutathione levels for enhanced photodynamic therapy[J]. Angew Chem Int Ed,2016,55(38):11467−11471. doi: 10.1002/anie.201605509