Top

Published in:

20-11-2020 | Chemical routes to materials

Polyoxomolybdates as efficient catalysts for Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate under mild condition

Authors: Baijie Xu, Zhihao liu, Qiaofei Xu, Xiao Han, Xinyi Ma, Jiawei Wang, Thirumurthy Kannan, Pengtao Ma, Jingping Wang, Jingyang Niu

Published in: Journal of Materials Science | Issue 7/2021

Activate our intelligent search to find suitable subject content or patents.

search-config

AI-assisted search

Off

Abstract

The development of new heterogeneous catalysts for Knoevenagel condensation reaction is critical for practical applications. Herein, we prepared three organophosphonate-functionalized polyoxomolybdates, Cs₂Na₉H₉[{Co(H₂O)₄}(TeMo₆O₂₁)₂{Co(OOCCH₂NCH₂PO₃)₂}₃]·41H₂O (1), Cs₂Na₈[H₆{Co(H₂O)₄}₃(SeMo₆O₂₁)₂{Co(OOCCH₂NCH₂PO₃)₂}₃]·31H₂O (2) and Cs₂Na₉H₃[H₆{Ni(H₂O)₄}(SeMo₆O₂₁)₂{Ni(OOCCH₂NCH₂PO₃)₂}₃]·28H₂O (3), which exhibit high catalytic activity for gram-scale Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate. Especially, under the optimal conditions, compound 1 can achieve a satisfactory yield (98%) and show high TON value (1960), which is superior to that of compounds 2 and 3. Notably, the TON value is much higher than that of previously reported catalysts. Such high catalytic performance could be attributed to the co-existence of Lewis acid and Lewis base sites in catalysts. In addition, based on substrates screening and recyclability tests, 1 has exhibited broad catalytic generality and good recyclability.

Graphical abstract

previous article Template-free synthesis of high specific surface area gauze-like porous graphitic carbon nitride for efficient photocatalytic degradation of tetracycline hydrochloride

next article A low temperature catalytic-type combustible gas sensor based on Pt supported zeolite catalyst films

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

inform now

Available only for authorised users

Miras HN, Yan J, Long D-L, Cronin L (2012) Engineering polyoxometalates with emergent properties. Chem Soc Rev 41:7403–7430. https://doi.org/10.1039/c2cs35190kCrossRef

Wang J, Niu Y, Zhang M et al (2018) Organophosphonate-functionalized lanthanopolyoxomolybdate: synthesis, characterization, magnetism, luminescence, and catalysis of H₂O₂-based thioether oxidation. Inorg Chem 57:1796–1805. https://doi.org/10.1021/acs.inorgchem.7b02672CrossRef

Singh V, Zhang Y, Yang L et al (2017) Two new tetravacant organometallic keggin-type heteropolyoxomolybdates-supported manganese carbonyl derivatives. Molecules 22:1351. https://doi.org/10.3390/molecules22081351CrossRef

Schwarz B, Streb C (2015) Architectural control of urea in supramolecular 1D strontium vanadium oxide chains. Dalton Trans 44:4195–4199. https://doi.org/10.1039/C4DT03691CCrossRef

Proust A, Matt B, Villanneau R et al (2012) Functionalization and post-functionalization: a step towards polyoxometalate-based materials. Chem Soc Rev 41:7605–7622. https://doi.org/10.1039/c2cs35119fCrossRef

Lu J, Ma X, Singh V et al (2018a) An isotetramolybdate-supported rhenium carbonyl derivative: synthesis, characterization, and use as a catalyst for sulfoxidation. Dalton Trans 47:5279–5285. https://doi.org/10.1039/C8DT00429CCrossRef

Kozhevnikov IV (1998) Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions. Chem Rev 98:171–198. https://doi.org/10.1021/cr960400yCrossRef

Sadakane M, Steckhan E (1998) Electrochemical properties of polyoxometalates as electrocatalysts. Chem Rev 98:219–238. https://doi.org/10.1021/cr960403aCrossRef

Xu Q, Li Y, Ban R et al (2018) Polyoxotungstates incorporated organophosphonate and nickel: synthesis, characterization and efficient catalysis for epoxidation of allylic alcohols. Dalton Trans 47:13479–13486. https://doi.org/10.1039/C8DT02590HCrossRef

10.

Wu H, Wan R, Si Y et al (2018) A helical chain-like organic–inorganic hybrid arsenotungstate with color-tunable photoluminescence. Dalton Trans 47:1958–1965. https://doi.org/10.1039/C7DT04608ACrossRef

11.

Wu H, Yan B, Li H et al (2018) Enhanced photostability luminescent properties of Er³⁺-doped near-white-emitting Dy_xEr_(1–_x₎-POM derivatives. Inorg Chem 57:7665–7675. https://doi.org/10.1021/acs.inorgchem.8b00674CrossRef

12.

Dou M-Y, Zhong D-D, Huang X-Q, Yang G-Y (2020) Imidazole-induced self-assembly of polyoxovanadate cluster organic framework for efficient Knoevenagel condensation under mild conditions. CrystEngComm 22:4147–4153. https://doi.org/10.1039/D0CE00660BCrossRef

13.

Han Q, Sun D, Zhao J et al (2019) A novel dicobalt-substituted tungstoantimonate polyoxometalate: synthesis, characterization, and photocatalytic water oxidation properties. Chin J Catal 40:953–958. https://doi.org/10.1016/S1872-2067(19)63358-9CrossRef

14.

Huang B, Ke D, Xiong Z et al (2020) Covalent hybrid materials between polyoxometalates and organic molecules for enhanced electrochemical properties. J Mater Sci 55:5554–5570. https://doi.org/10.1007/s10853-020-04404-0CrossRef

15.

Tian P, He X, Li W et al (2018) Zr-MOFs based on keggin-type polyoxometalates for photocatalytic hydrogen production. J Mater Sci 53:12016–12029. https://doi.org/10.1007/s10853-018-2476-0CrossRef

16.

Lu J, Ma X, Wang P et al (2019) Synthesis, characterization and catalytic epoxidation properties of a new tellurotungstate(iv)-supported rhenium carbonyl derivative. Dalton Trans 48:628–634. https://doi.org/10.1039/C8DT04195DCrossRef

17.

Lu J, Ma X, Singh V et al (2018b) Facile CO₂ cycloaddition to epoxides by using a tetracarbonyl metal selenotungstate derivate [{Mn(CO)₃}₄(Se₂W₁₁O₄₃)]^8–. Inorg Chem 57:14632–14643. https://doi.org/10.1021/acs.inorgchem.8b02321CrossRef

18.

Luo H, Wang L, Shang S et al (2019) Aerobic oxidative cleavage of 1,2-diols catalyzed by atomic-scale cobalt-based heterogeneous catalyst. Commun Chem 2:17–26. https://doi.org/10.1038/s42004-019-0116-5CrossRef

19.

Lee A, Michrowska A, Sulzer-Mosse S, List B (2011) The Catalytic asymmetric Knoevenagel condensation. Angew Chem Int Ed 50:1707–1710. https://doi.org/10.1002/anie.201006319CrossRef

20.

Jia Y, Fang Y, Zhang Y et al (2015) Classical keggin intercalated into layered double hydroxides: facile preparation and catalytic efficiency in Knoevenagel condensation reactions. Chem Eur J 21:14862–14870. https://doi.org/10.1002/chem.201501953CrossRef

21.

Moghaddam FM, Mirjafary Z, Javan MJ et al (2014) Facile synthesis of highly substituted 2-pyrone derivatives via a tandem Knoevenagel condensation/lactonization reaction of β-formyl-esters and 1,3-cyclohexadiones. Tetrahedron Lett 55:2908–2911. https://doi.org/10.1016/j.tetlet.2014.02.104CrossRef

22.

Mogharabi-Manzari M, Amini M, Abdollahi M et al (2018) Co-immobilization of laccase and TEMPO in the compartments of mesoporous silica for a green and one-pot cascade synthesis of coumarins by Knoevenagel condensation. ChemCatChem 10:1542–1546. https://doi.org/10.1002/cctc.201701527CrossRef

23.

Almáši M, Zeleňák V, Opanasenko M, Císařová I (2015) Ce(III) and Lu(III) metal–organic frameworks with Lewis acid metal sites: preparation, sorption properties and catalytic activity in Knoevenagel condensation. Catal Today 243:184–194. https://doi.org/10.1016/j.cattod.2014.07.028CrossRef

24.

Huang A, Nie R, Zhang B et al (2020) Tandem condensation-hydrogenation to produce alkylated nitriles using bifunctional catalysts: platinum nanoparticles supported on MOF-derived carbon. ChemCatChem 12:602–608. https://doi.org/10.1002/cctc.201901930CrossRef

25.

Rashed MdN, Touchy AS, Chaudhari C et al (2020) Selective C3-alkenylation of oxindole with aldehydes using heterogeneous CeO₂ catalyst. Chin J Catal 41:970–976. https://doi.org/10.1016/S1872-2067(19)63515-1CrossRef

26.

Schneider EM, Zeltner M, Kränzlin N et al (2015) Base-free Knoevenagel condensation catalyzed by copper metal surfaces. Chem Commun 51:10695–10698. https://doi.org/10.1039/C5CC02541ACrossRef

27.

Ono Y (2003) Solid base catalysts for the synthesis of fine chemicals. J Catal 216:406–415. https://doi.org/10.1016/S0021-9517(02)00120-3CrossRef

28.

Tietze LF (1996) Domino reactions in organic synthesis. Chem Rev 96:115–136. https://doi.org/10.1021/cr950027eCrossRef

29.

Acker DS, Hertler WR (1962) Substituted quinodimethans. I. Preparation and chemistry of 7,7,8,8-Tetracyanoquinodimethan. J Am Chem Soc 84:3370–3374. https://doi.org/10.1021/ja00876a028CrossRef

30.

Santamarta F, Verdia P, Tojo E (2008) A simple, efficient and green procedure for Knoevenagel reaction in [MMIm][MSO₄] Ionic liquid. Catal Commun 9:1779–1781. https://doi.org/10.1016/j.catcom.2008.02.010CrossRef

31.

Aider N, Smuszkiewicz A, Pérez-Mayoral E et al (2014) Amino-grafted SBA-15 material as dual acid–base catalyst for the synthesis of coumarin derivatives. Catal Today 227:215–222. https://doi.org/10.1016/j.cattod.2013.10.016CrossRef

32.

Farzaneh F, Kashani Maleki M, Ghandi M (2016) Multifunctional Cu(II) organic–inorganic hybrid as a catalyst for Knoevenagel condensation. Reac Kinet Mech Cat 117:87–101. https://doi.org/10.1007/s11144-015-0919-zCrossRef

33.

Reddy BM, Patil MK, Rao KN, Reddy GK (2006) An easy-to-use heterogeneous promoted zirconia catalyst for Knoevenagel condensation in liquid phase under solvent-free conditions. J Mol Catal A Chem 258:302–307. https://doi.org/10.1016/j.molcata.2006.05.065CrossRef

34.

Tanabe T, Yamada Y, Kim J et al (2016) Knoevenagel condensation using nitrogen-doped carbon catalysts. Carbon 109:208–220. https://doi.org/10.1016/j.carbon.2016.08.003CrossRef

35.

Li G, Xiao J, Zhang W (2012) Efficient and reusable amine-functionalized polyacrylonitrile fiber catalysts for Knoevenagel condensation in water. Green Chem 14:2234–2242. https://doi.org/10.1039/c2gc35483gCrossRef

36.

Martins L, Hölderich W, Hammer P, Cardoso D (2010) Preparation of different basic Si–MCM-41 catalysts and application in the Knoevenagel and Claisen-Schmidt condensation reactions. J Catal 271:220–227. https://doi.org/10.1016/j.jcat.2010.01.015CrossRef

37.

Utting KA, Macquarrie DJ (2000) Silica-supported imines as mild, efficient base catalysts. New J Chem 24:591–595. https://doi.org/10.1039/b002424oCrossRef

38.

Opanasenko M, Dhakshinamoorthy A, Shamzhy M et al (2013) Comparison of the catalytic activity of MOFs and zeolites in Knoevenagel condensation. Catal Sci Technol 3:500–507. https://doi.org/10.1039/C2CY20586FCrossRef

39.

Zhang Y, Zhang J, Tian M et al (2016) Fabrication of amino-functionalized Fe₃O₄@Cu₃(BTC)₂ for heterogeneous Knoevenagel condensation. Chin J Catal 37:420–427. https://doi.org/10.1016/S1872-2067(15)61013-0CrossRef

40.

Zhang Y, Dai T, Zhang F et al (2016) Fe₃O₄@UiO-66-NH₂ core–shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation. Chin J Catal 37:2106–2113. https://doi.org/10.1016/S1872-2067(16)62562-7CrossRef

41.

Guo C, Zhang Y, Zhang L et al (2018) 2-Methylimidazole-assisted synthesis of a two-dimensional MOF-5 catalyst with enhanced catalytic activity for the Knoevenagel condensation reaction. CrystEngComm 20:5327–5331. https://doi.org/10.1039/C8CE00954FCrossRef

42.

Hu H, Yan Q, Ge R, Gao Y (2018) Covalent organic frameworks as heterogeneous catalysts. Chin J Catal 39:1167–1179. https://doi.org/10.1016/S1872-2067(18)63057-8CrossRef

43.

Rana S, Jonnalagadda SB (2017) Synthesis and characterization of amine functionalized graphene oxide and scope as catalyst for Knoevenagel condensation reaction. Catal Commun 92:31–34. https://doi.org/10.1016/j.catcom.2016.12.023CrossRef

44.

Wada S, Suzuki H (2003) Calcite and fluorite as catalyst for the Knövenagel condensation of malononitrile and methyl cyanoacetate under solvent-free conditions. Tetrahedron Lett 44:399–401. https://doi.org/10.1016/S0040-4039(02)02431-0CrossRef

45.

Narasimharao K, Mokhtar M, Basahel SN, Al-Thabaiti SA (2013) Synthesis, characterization, and catalytic activity of nitridated magnesium silicate catalysts. J Mater Sci 48:4274–4283. https://doi.org/10.1007/s10853-013-7241-9CrossRef

46.

Appaturi JN, Selvaraj M, Abdul Hamid SB (2018) Synthesis of 3-(2-furylmethylene)-2,4-pentanedione using DL-Alanine functionalized MCM-41 catalyst via Knoevenagel condensation reaction. Microporous Mesoporous Mater 260:260–269. https://doi.org/10.1016/j.micromeso.2017.03.031CrossRef

47.

Khoshnavazi R, Bahrami L, Havasi F (2016) Organic–inorganic hybrid polyoxometalate and its graphene oxide–Fe₃O₄ nanocomposite, synthesis, characterization and their applications as nanocatalysts for the Knoevenagel condensation and the synthesis of 2,3-dihydroquinazolin-4(1H)-ones. RSC Adv 6:100962–100975. https://doi.org/10.1039/C6RA15339ACrossRef

48.

Yoshida A, Hikichi S, Mizuno N (2007) Acid–base catalyses by dimeric disilicoicosatungstates and divacant γ-Keggin-type silicodecatungstate parent: reactivity of the polyoxometalate compounds controlled by step-by-step protonation of lacunary WO sites. J Org Chem 692:455–459. https://doi.org/10.1016/j.jorganchem.2006.05.061CrossRef

49.

Sugahara K, Kimura T, Kamata K et al (2012) A highly negatively charged γ-Keggin germanodecatungstate efficient for Knoevenagel condensation. Chem Commun 48:8422–8424. https://doi.org/10.1039/c2cc33839dCrossRef

50.

Zhao S, Chen Y, Song Y-F (2014) Tri-lacunary polyoxometalates of Na₈H[PW₉O₃₄] as heterogeneous Lewis base catalysts for Knoevenagel condensation, cyanosilylation and the synthesis of benzoxazole derivatives. Appl Catal A Gen 475:140–146. https://doi.org/10.1016/j.apcata.2014.01.017CrossRef

51.

Hayashi S, Yamazoe S, Koyasu K, Tsukuda T (2016) Application of group V polyoxometalate as an efficient base catalyst: a case study of decaniobate clusters. RSC Adv 6:16239–16242. https://doi.org/10.1039/C6RA00338ACrossRef

52.

Gutierrez LF, Nope E, Rojas HA et al (2018) New application of decaniobate salt as basic solid in the synthesis of 4H-pyrans by microwave assisted multicomponent reactions. Res Chem Intermed 44:5559–5568. https://doi.org/10.1007/s11164-018-3440-yCrossRef

53.

Ge W, Wang X, Zhang L et al (2016) Fully-occupied Keggin type polyoxometalate as solid base for catalyzing CO₂ cycloaddition and Knoevenagel condensation. Catal Sci Technol 6:460–467. https://doi.org/10.1039/C5CY01038ACrossRef

54.

Xu Q, Niu Y, Wang G et al (2018) Polyoxoniobates as a superior Lewis base efficiently catalyzed Knoevenagel condensation. Mol Catal 453:93–99. https://doi.org/10.1016/j.mcat.2018.05.002CrossRef

55.

Hayashi S, Sasaki N, Yamazoe S, Tsukuda T (2018) Superior base catalysis of group 5 hexametalates [M₆O₁₉]^8– (M=Ta, Nb) over group 6 hexametalates [M₆O₁₉]^2– (M=Mo, W). J Phys Chem C 122:29398–29404. https://doi.org/10.1021/acs.jpcc.8b10400CrossRef

56.

Calvino-Casilda V, Olejniczak M, Martín-Aranda RM, Ziolek M (2016) The role of metallic modifiers of SBA-15 supports for propyl-amines on activity and selectivity in the Knoevenagel reactions. Microporous Mesoporous Mater 224:201–207. https://doi.org/10.1016/j.micromeso.2015.11.027CrossRef

57.

Yang Y, Yao H-F, Xi F-G, Gao E-Q (2014) Amino-functionalized Zr(IV) metal–organic framework as bifunctional acid–base catalyst for Knoevenagel condensation. J Mol Catal A Chem 390:198–205. https://doi.org/10.1016/j.molcata.2014.04.002CrossRef

58.

Tran UPN, Le KKA, Phan NTS (2011) Expanding applications of metal-organic frameworks: zeolite imidazolate framework ZIF-8 as an efficient heterogeneous catalyst for the Knoevenagel reaction. ACS Catal 1:120–127. https://doi.org/10.1021/cs1000625CrossRef

59.

Xia Y, Mokaya R (2003) Highly ordered mesoporous silicon oxynitride materials as base catalysts. Angew Chem Int Ed 42:2639–2644. https://doi.org/10.1002/anie.200350978CrossRef

60.

Otomo R, Osuga R, Kondo JN et al (2019) Cs-Beta with an Al-rich composition as a highly active base catalyst for Knoevenagel condensation. Appl Catal A Gen 575:20–24. https://doi.org/10.1016/j.apcata.2019.02.014CrossRef

61.

Yue L-J, Liu Y-Y, Xu G-H, Ma J-F (2019) Calix[4]arene-based polyoxometalate organic–inorganic hybrid and coordination polymer as heterogeneous catalysts for azide–alkyne cycloaddition and Knoevenagel condensation reaction. New J Chem 43:15871–15878. https://doi.org/10.1039/C9NJ03930ACrossRef

62.

Jia H, Zhao Y, Niu P et al (2018) Amine-functionalized MgAl LDH nanosheets as efficient solid base catalysts for Knoevenagel condensation. Mol Catal 449:31–37. https://doi.org/10.1016/j.mcat.2018.02.004CrossRef

63.

Natour S, Omar S, Abu-Reziq R (2015) Catalysis with solid lipid particles. J Mater Sci 50:2747–2758. https://doi.org/10.1007/s10853-015-8830-6CrossRef

64.

Xing S, Li J, Niu G et al (2018) Chiral and amine groups functionalized polyoxometalate-based metal-organic frameworks for synergic catalysis in aldol and Knoevenagel condensations. Mol Catal 458:83–88. https://doi.org/10.1016/j.mcat.2018.08.011CrossRef

65.

Elhamifar D, Kazempoor S, Karimi B (2016) Amine-functionalized ionic liquid-based mesoporous organosilica as a highly efficient nanocatalyst for the Knoevenagel condensation. Catal Sci Technol 6:4318–4326. https://doi.org/10.1039/C5CY01666ECrossRef

66.

Panja SK, Dwivedi N, Saha S (2015) First report of the application of simple molecular complexes as organo-catalysts for Knoevenagel condensation. RSC Adv 5:65526–65531. https://doi.org/10.1039/C5RA09036ACrossRef

67.

Miao Z, Luan Y, Qi C, Ramella D (2016) The synthesis of a bifunctional copper metal organic framework and its application in the aerobic oxidation/Knoevenagel condensation sequential reaction. Dalton Trans 45:13917–13924. https://doi.org/10.1039/C6DT01690ACrossRef

Title: Polyoxomolybdates as efficient catalysts for Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate under mild condition
Authors: Baijie Xu
Zhihao liu
Qiaofei Xu
Xiao Han
Xinyi Ma
Jiawei Wang
Thirumurthy Kannan
Pengtao Ma
Jingping Wang
Jingyang Niu
Publication date: 20-11-2020
Publisher: Springer US
Published in: Journal of Materials Science / Issue 7/2021
Print ISSN: 0022-2461
Electronic ISSN: 1573-4803
DOI: https://doi.org/10.1007/s10853-020-05562-x

Springer Professional

Abstract

Graphical abstract

Please log in to get access to your license.

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Springer Professional "Technik"

Other articles of this Issue 7/2021

Whispering-gallery mode resonance-assisted plasmonic sensing and switching in subwavelength nanostructures

Exploration of nontrivial topological domain structures in the equilibrium state of magnetic nanodisks

NADPH-guided synthesis of iodide-responsive nanozyme: synergistic effects in nanocluster growth and peroxidase-like activity

Preparation of PEO-based Cu2O/Bi2O2CO3 electrospun fibrous membrane toward enhanced photocatalytic degradation of chloramphenicol

Influence of alloying on the tensile strength and electrical resistivity of silver nanowire: copper composites macroscopic wires

Sulfur quantum dot-based portable paper sensors for fluorometric and colorimetric dual-channel detection of cobalt

Premium Partners