Generic placeholder image

Current Catalysis


ISSN (Print): 2211-5447
ISSN (Online): 2211-5455

Research Article

MgRuAl-layered Double Hydroxides (LDH): An Efficient Multifunctional Catalyst for Aldol Condensation and Transfer Hydrogenation Reactions

Author(s): Hemaprobha Saikia and Sanjay Basumatary*

Volume 8, Issue 1, 2019

Page: [62 - 69] Pages: 8

DOI: 10.2174/2211550108666190418125857


Background: Layered double hydroxides (LDH) are drawing much attention as solid catalysts in recent years and have applications in various organic transformations as they possess a variety of basic sites which could be obtained by exchange of metal ions or by intercalation of suitable anions into their interlayer space. Ru based complexes have widespread catalytic applications in many organic reactions. Herein, novel ruthenium containing ternary LDH has been synthesized and used as a multifunctional catalyst for Aldol condensation and transfer hydrogenation reactions.

Methods: Ternary LDH multifunctional catalyst containing Mg, Ru and Al was prepared by coprecipitation and hydrothermal treatment. The catalyst was characterized by elemental analysis, Powder XRD, FT-IR, BET, TGA, DRS, SEM, EDX, XPS and TEM. The products of the reactions were characterized by 1H NMR and GC-MS.

Results: The analysis of catalyst revealed incorporation of Ru in the brucite layers of the LDH and showed the mosaic single crystal with BET surface area of 84.25 m2 g-1. This catalyst yielded 85–98% products for Aldol condensation reactions within 4 h reaction time, and 82–98% products for transfer hydrogenation reactions within 16 h reaction time.

Conclusion: The resultant MgRuAl-LDH with acid and base sites was found to be highly active and selective for one-step synthesis of nitrile compounds. The catalyst works more efficiently for Aldol condensation reactions in shorter reaction times compared to transfer hydrogenation reactions.

Keywords: MgRuAl-LDH, aldol condensation, transfer hydrogenation, nitrile compounds, hydroxide, condensation.

« Previous
Graphical Abstract
Kuang, Y.; Zhao, L.; Zhang, S.; Zhang, F.; Dong, M.; Xu, S. Morphologies, preparations and applications of layered double hydroxide micro-/nanostructures. Materials , 2010, 3, 5220-5235.
Rives, V.; Ulibarri, M.A. Layered double hydroxides (LDH) intercalated with metal coordination compounds and oxometalates. Coord. Chem. Rev., 1999, 181, 61-120.
King, A.G.; Keswani, S.T. Colloid mills: Theory and experiment. J. Am. Ceram. Soc., 1994, 77, 769-777.
Gunawan, P.; Xu, R. Direct assembly of anisotropic layered double hydroxide (LDH) nanocrystals on spherical template for fabrication of drug-LDH hollow nanospheres. Chem. Mater., 2009, 21, 781-783.
Zhang, L.H.; Li, F.; Evans, D.G.; Duan, X. Cu-Zn-(Mn)-(Fe)-Al layered double hydroxides and their mixed metal oxides: Physicochemical and catalytic properties in wet hydrogen peroxide oxidation of phenol. Ind. Eng. Chem. Res., 2010, 49, 5959-5968.
Coronado, E.; Martí-Gastaldo, C.; Navarro-Moratalla, E.; Ribera, A. Confined growth of cyanide-based magnets in two dimensions. Inorg. Chem., 2010, 49, 1313-1315.
Jaubertie, C.; Holgado, M.J.; San Roman, M.S.; Rives, V. Structural characterization and delamination of lactate-intercalated Zn, Al-layered double hydroxides. Chem. Mater., 2006, 18, 3114-3121.
Motokura, K.; Nishimura, D.; Mori, K.; Mizugaki, T.; Ebitani, K.; Kaneda, K. A ruthenium-grafted hydrotalcite as a multifunctional catalyst for direct α-alkylation of nitriles with primary alcohols. J. Am. Chem. Soc., 2004, 126, 5662-5663.
Fürstner, A. Olefin metathesis and beyond. Angew. Chem., 2000, 39, 3012-3043.
Deshmukh, P.H.; Bechert, S. Alkene metathesis: The search for better catalysts. Dalton Trans., 2007, 24, 2479-2491.
Gonzalez, S.D.; Nolan, S.P. Stereoelectronic parameters associated with N-heterocyclic carbene (NHC) ligands: A quest for understanding. Coord. Chem. Rev., 2007, 251, 874-883.
Lam, F.L.; Kwong, F.Y.; Chan, A.S.C. Chiral phosphorous ligands with interesting properties and practical applications. Topics Organomet. Chem. 36; , 2011. Springer, Berlin, Heidelberg.
Corma, A.; Garcia, H. Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems. Chem. Rev., 2002, 102, 3837-3892.
Monteil, F.; Queau, R.; Kalck, P. Behaviour of water-soluble dinuclear rhodium complexes in the hydroformylation reaction of oct-1-ene. J. Organomet. Chem., 1994, 480, 177-184.
Cornils, B. Industrial aqueous biphasic catalysis: Status and directions. Org. Process Res. Dev., 1998, 2, 121-127.
Kaneda, K.; Yamashita, T.; Matsushita, T.; Ebitani, K. Heterogeneous oxidation of allylic and benzylic alcohols catalyzed by Ru-Al-Mg hydrotalcites in the presence of molecular oxygen. J. Org. Chem., 1998, 63, 1750-1751.
Choudary, B.M.; Chowdari, N.S.; Madhi, S.; Kantam, M.L. A trifunctional catalyst for one-pot synthesis of chiral diols via heck coupling-N-oxidation-asymmetric dihydroxylation: Application for the synthesis of diltiazem and Taxol side chain. J. Org. Chem., 2003, 68, 1736-1746.
Choudary, B.M.; Kantam, M.L.; Kavita, B.; Reddy, C.V.; Rao, K.K.; Figueras, F. Aldol condensations catalysed by novel Mg-Al-O-t-Bu hydrotalcite. Tetrahedron Lett., 1998, 39, 3555-3558.
Choudary, B.M.; Sridhar, C.; Kantam, M.L.; Venkanna, G.T.; Sreedhar, B. Design and evolution of copper apatite catalysts for N-arylation of heterocycles with chloro- and fluoro- arenes. J. Am. Chem. Soc., 2005, 127, 9948-9949.
Yamaguchi, K.; Mori, K.; Mizugaki, T.; Ebitani, K.; Kaneda, K. Epoxidation of α, β-unsaturated ketones using hydrogen peroxide in the presence of basic hydrotalcite catalysts. J. Org. Chem., 2000, 65, 6897-6903.
De Vos, D.E.; Dams, M.; Sels, B.F.; Jacobs, P.A. Ordered mesoporous and microporous molecular sieves functionalized with transition metal complexes as catalysts for selective organic transformations. Chem. Rev., 2002, 102, 3615-3640.
Kulp, S.S.; McGee, M.J. Oxidative decyanation of benzyl and benzhydryl cyanides: A simplified procedure. J. Org. Chem., 1983, 48, 4097-4098.
Hartmann, R.W.; Batzl, C. Aromatase inhibitors. Synthesis and evaluation of mammary tumor inhibiting activity of 3-alkylated 3-(4-aminophenyl) piperidine-2, 6-diones. Med. Chem. , 1986, 29, 1362-1369.
Takaya, H.; Yoshida, K.; Isozaki, K.; Terai, H.; Murahashi, S.I. Transition-metal-based Lewis acid and base ambiphilic catalysts of iridium hydride complexes: Multicomponent synthesis of glutarimides. Angew. Chem., 2003, 42, 3302-3304.
Inagaki, S.; Fukushima, Y.; Kuroda, K. Synthesis of highly ordered mesoporous materials from a layered polysilicate. J. Chem. Soc. Chem. Commun., 1993, 8, 680-682.
Sharma, S.K.; Parikh, P.A.; Jasra, R.V. Ruthenium containing hydrotalcite as a solid base catalyst for >C=C< double bond isomerization in perfumery chemicals. J. Mol. Catal., 2010, 317, 27-33.
del Arco, M.; Gutierrez, S.; Martin, C.; Rives, V. Intercalation of [Cr(C2O4)3] complex in Mg, Al layered double hydroxides. Inorg. Chem., 2003, 42, 4232-4240.
Gomez-Romero, P. Hybrid organic–inorganic materials-In search of synergic activity. Adv. Mater., 2001, 13, 163-174.
Cavani, F.; Trifiro, F.; Vaccari, A. Hydrotalcite-type anionic clays: Preparation, properties and applications. Catal. Today, 1991, 11, 173-301.
Abello, S.; Medina, F.; Tichit, D.; Ramirez, J.P.; Groen, J.C.; Sueiras, J.E.; Salagre, P.; Cesteros, Y. Aldol condensations over reconstructed Mg-Al hydrotalcites: Structure–activity relationships related to the rehydration method. Chemistry Eur. J, 2005, 11, 728-739.
Kim, K.S.; Winograd, N. X-Ray photoelectron spectroscopic studies of ruthenium-oxygen surfaces. J. Catal., 1974, 35, 66-72.
Citrin, P.H.; Ginsbeg, A.P. X-ray photoemission from the Creutz-Taube mixed valence complex: A reassessment. J. Am. Chem. Soc., 1981, 103, 3673-3679.

Rights & Permissions Print Cite
© 2024 Bentham Science Publishers | Privacy Policy