Superior performance of metal-organic frameworks over zeolites as solid acid catalysts in the Prins reaction: green synthesis of nopol.

The catalytic performance of a set of metal-organic frameworks [CuBTC, FeBTC, MIL-100(Fe), MIL-100(Cr), ZIF-8, MIL-53(Al)] was investigated in the Prins condensation of β-pinene with formaldehyde and compared with the catalytic behavior of conventional aluminosilicate zeolites BEA and FAU and titanosilicate zeolite MFI (TS-1). The activity of the investigated metal-organic frameworks (MOFs) increased with the increasing concentration of accessible Lewis acid sites in the order ZIF-8<MIL-53(Al)<FeBTC<MIL-100(Cr)<MIL-100(Fe). Unwanted β-pinene-like isomerization takes place on the strong Brønsted acid sites of zeolites BEA and FAU, which showed significantly lower selectivity to the target nopol than the MOFs. Its high activity, the preservation of its structure and active sites, and the possibility to use it in at least three catalytic cycles without loss of activity make MIL-100 (Fe) the best performing catalyst of the series for the Prins condensation of β-pinene and paraformaldehyde. Our report exemplifies the advantages of MOFs over zeolites as solid catalysts in liquid-phase reactions for the production of fine chemicals.

[1]  J. Čejka,et al.  The effect of substrate size in the Beckmann rearrangement: MOFs vs. zeolites , 2013 .

[2]  J. Čejka,et al.  Comparison of the catalytic activity of MOFs and zeolites in Knoevenagel condensation , 2013 .

[3]  J. Čejka,et al.  Application of Molecular Sieves in Transformations of Biomass and Biomass-Derived Feedstocks , 2013 .

[4]  Ana E. Platero‐Prats,et al.  Green Microwave Synthesis of MIL‐100(Al, Cr, Fe) Nanoparticles for Thin‐Film Elaboration , 2012 .

[5]  B. Louis,et al.  Design of Scandium-Doped USY Zeolite: An Efficient and Green Catalyst for Aza-Diels–Alder Reaction , 2012 .

[6]  G. Chuah,et al.  Mesoporous Zr-SBA-15 as a green solid acid catalyst for the Prins reaction , 2012 .

[7]  J. Čejka,et al.  Synthesis of quinolines via Friedländer reaction catalyzed by CuBTC metal-organic-framework. , 2012, Dalton transactions.

[8]  Jiří Čejka,et al.  Zeolite-based materials for novel catalytic applications: Opportunities, perspectives and open problems , 2012 .

[9]  J. Mota,et al.  Experimental and Theoretical Studies of Supercritical Methane Adsorption in the MIL-53(Al) Metal Organic Framework , 2011 .

[10]  Avelino Corma,et al.  Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes , 2011 .

[11]  Weiming Hua,et al.  Acidity and porosity modulation of MWW type zeolites for Nopol production by Prins condensation , 2011 .

[12]  Siglinda Perathoner,et al.  Creating and mastering nano-objects to design advanced catalytic materials , 2011 .

[13]  A. Corma,et al.  Delineating similarities and dissimilarities in the use of metal organic frameworks and zeolites as heterogeneous catalysts for organic reactions. , 2011, Dalton transactions.

[14]  J. Čejka,et al.  Two-dimensional zeolites: dream or reality? , 2011 .

[15]  A. Villa,et al.  Nopol production over Sn-MCM-41 synthesized by different procedures – Solvent effects , 2010 .

[16]  D. Farrusseng,et al.  Investigation of Acid Centers in MIL‐53(Al, Ga) for Brønsted‐Type Catalysis: In Situ FTIR and Ab Initio Molecular Modeling , 2010 .

[17]  P. K. Sinha,et al.  Highly selective and clean synthesis of nopol over well-ordered mesoporous tin silicate catalysts , 2010 .

[18]  C. Serre,et al.  Controlled reducibility of a metal-organic framework with coordinatively unsaturated sites for preferential gas sorption. , 2010, Angewandte Chemie.

[19]  A. Corma,et al.  Engineering metal organic frameworks for heterogeneous catalysis. , 2010, Chemical reviews.

[20]  J. Čejka,et al.  Recent Advances in Catalysis Over Mesoporous Molecular Sieves , 2010 .

[21]  Youngson Choe,et al.  Well ordered two-dimensional SnSBA-15 catalysts synthesized with high levels of tetrahedral tin for highly efficient and clean synthesis of nopol , 2010 .

[22]  S. Abelló,et al.  Zeolite Catalysts with Tunable Hierarchy Factor by Pore‐Growth Moderators , 2009 .

[23]  J. Caro,et al.  Zeolitic imidazolate framework membrane with molecular sieving properties by microwave-assisted solvothermal synthesis. , 2009, Journal of the American Chemical Society.

[24]  J. Čejka,et al.  The role of the zeolite channel architecture and acidity on the activity and selectivity in aromatic transformations: The effect of zeolite cages in SSZ-35 zeolite , 2009 .

[25]  A. Villa,et al.  Characterization of Sn- and Zn-loaded MCM-41 catalysts for nopol synthesis , 2009 .

[26]  M. Clarke.  The carbonyl ene reaction , 2008 .

[27]  Gérard Férey,et al.  Hybrid porous solids: past, present, future. , 2008, Chemical Society reviews.

[28]  M. Yadav,et al.  Prins condensation for synthesis of nopol from β-pinene and paraformaldehyde on novel Fe–Zn double metal cyanide solid acid catalyst , 2007 .

[29]  C. Serre,et al.  Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores. , 2007, Chemical communications.

[30]  Isidro M. Pastor and Miguel Yus.  The Prins Reaction: Advances and Applications , 2007 .

[31]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[32]  M. Yadav,et al.  Synthesis of nopol from β-pinene using ZnCl2 impregnated Indian Montmorillonite , 2006 .

[33]  S. Kawi,et al.  Highly selective synthesis of nopol over mesoporous and microporous solid acid catalysts , 2006 .

[34]  Edwin A. Alarcón,et al.  Nopol synthesis over Sn-MCM-41 and sn-kenyaite catalysts , 2005 .

[35]  Gérard Férey,et al.  A hybrid solid with giant pores prepared by a combination of targeted chemistry, simulation, and powder diffraction. , 2004, Angewandte Chemie.

[36]  J. Suo,et al.  Wells–Dawson type molybdovanadophosphoric heteropolyacids catalyzed Prins cyclization of alkenes with paraformaldehyde under mild conditions—a facile and efficient method to 1,3-dioxane derivatives , 2004 .

[37]  U. R. Pillai,et al.  Mesoporous iron phosphate as an active, selective and recyclable catalyst for the synthesis of nopol by Prins condensation. , 2004, Chemical communications.

[38]  Gérard Férey,et al.  A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration. , 2004, Chemistry.

[39]  Mark E. Davis,et al.  Issues in the synthesis of crystalline molecular sieves: towards the crystallization of low framework-density structures. , 2004, Chemphyschem : a European journal of chemical physics and physical chemistry.

[40]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[41]  J. Greneche,et al.  Synthesis, structure, and Mössbauer study of [Fe(H2O)(2)(C(9)O(6)H4)].H2O: a two-dimensional iron(II) trimellitate (MIL-67). , 2003, Inorganic chemistry.

[42]  J. Yadav,et al.  InBr3–[bmim]PF6: a novel and recyclable catalytic system for the synthesis of 1,3-dioxane derivatives , 2003 .

[43]  Edwin A. Alarcón,et al.  Synthesis of nopol over MCM-41 catalysts. , 2002, Chemical communications.

[44]  J. Snaith,et al.  Synthesis of 3,4-disubstituted piperidines by carbonyl ene and Prins cyclizations: a switch in diastereoselectivity between Lewis and Brønsted acid catalysts. , 2002, Organic letters.

[45]  M. Riou-Cavellec,et al.  A new three-dimensional iron trimesate: [Fe3(H2O)5(C9O6H3)2·3H2O] or MIL-65 , 2002 .

[46]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[47]  R. Sheldon,et al.  Heterogeneous Catalysts for Liquid-Phase Oxidations: Philosophers' Stones or Trojan Horses? , 1998 .

[48]  Avelino Corma,et al.  Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions , 1995 .

[49]  E. Bacon,et al.  Intramolecular olefinic aldehyde Prins reactions for the construction of five-membered rings , 1985 .

[50]  G. Phillips,et al.  Ethylaluminum dichloride catalyzed ene reactions of aldehydes with nonnucleophilic alkenes , 1983 .

[51]  M. Brechbiel,et al.  Observations on the mechanism of the Lewis acid catalyzed ene reaction , 1982 .

[52]  M. Orfanopoulos,et al.  Changes in ene reaction mechanisms with Lewis acid catalysis , 1981 .

[53]  J. P. Bain.  Nopol. I. The Reaction of β-Pinene with Formaldehyde , 1946 .

[54]  B. Snider.  The Prins and Carbonyl Ene Reactions , 1991 .