Oxidation of the lignin model monomer apocynol, 1-(4-hydroxy-3-methoxyphenoxy)-ethanol catalysed by mesoporous silica catalysts i.e. MCM-41, MCM-48, SBA-15 using H2O2 as an oxidant has been studied. Selectively, 2-methoxybenzoquinone was obtained along with acetovanillone. Such unprecedented oxidation behaviour of these metal free siliceous catalysts is attributed to the polar internal surface, high surface area as well as the pore architecture. On the other hand, the studied reaction was found to be non-selective when a commercial grade mesoporous silica i.e. Silica-5 was used as catalyst for comparison. Among the various silica catalysts studied, MCMs gave highest conversion and selectivity towards 2-methoxybenzoquinone under very mild reaction conditions.
References
[1]
Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz, M.E., Kresge, C.T., Schmitt, K.D., Chu, C.T.W., Olson, D.H., Sheppard, E.W., McCullen, S.B., Higgins, J.B. and Schlenker, J.L. (1992) A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates. Journal of the American Chemical Society, 114, 10834-10843.
http://dx.doi.org/10.1021/ja00053a020
[2]
Fryxell, G.E. and Liu, J. (2000) Adsorption on Silica Surfaces. In: Papirer, E., Ed., Designing Surface Chemistry in Mesoporous Silica, Marcel Dekker, Inc., New York.
[3]
Cao, G. (2004) Nanostructures and Nanomaterials. Synthesis, Properties, and Applications. Imperial College Press, London. http://dx.doi.org/10.1142/9781860945960
[4]
Zhao, D., Huo, Q., Feng, J., Chmelka, B.F. and Stucky, G.D. (1998) Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures. Journal of the American Chemical Society 120, 6024-6036. http://dx.doi.org/10.1021/ja974025i
[5]
Selvam, P. and Dapurkar, S.E. (2004) Catalytic Activity of Highly Ordered Mesoporous VMCM-48. Applied Catalysis A: General, 276, 257-265. http://dx.doi.org/10.1016/j.apcata.2004.08.012
[6]
Marasas, L.W. and Harrington, J.S. (1960) Some Oxidative and Hydroxylative Actions of Quartz: Their Possible Relationship to the Development of Silicosis. Nature, 188, 1173-1174. http://dx.doi.org/10.1038/1881173a0
[7]
Schofield, P.J., Ralph, B.J. and Green, J.H. (1964) Mechanisms of Hydroxylation of Aromatics on Silica Surfaces. Journal of Physical Chemistry, 68, 472-476. http://dx.doi.org/10.1021/j100785a006
[8]
Itoh, A., Kodama, T., Masuki, Y. and Inagaki, S. (2006) Oxidative Photo-Decarboxylation in the Presence of Mesoporous Silicas. Chemical and Pharmaceutical Bulletin, 54, 1571-1575. http://dx.doi.org/10.1248/cpb.54.1571
[9]
Badamali, S.K., Luque, R., Clark, J.H. and Breeden, S.W. (2013) Unprecedented Oxidative Properties of Mesoporous Silica Materials: Towards Microwave-Assisted Oxidation of Lignin Model Compounds. Catalysis Communications, 31, 1-4. http://dx.doi.org/10.1016/j.catcom.2012.11.006
[10]
Badamali, S.K., Clark, J.H. and Breeden, S.W. (2008) Microwave Assisted Selective Oxidation of Lignin Model Phenolic Monomer over SBA-15. Catalysis Communications, 9, 2168-2170.
http://dx.doi.org/10.1016/j.catcom.2008.04.012
[11]
Holladay, J.E., Bozell, J.J., White, J.F. and Johnson, D. (2007) Top Value-Added Chemicals from Biomass, Results of Screening for Potential Candidates from Biorefinery Lignin, II, USDOE, PNNL-16983.
[12]
Wozniak, J.C., Dimmel, D.R. and Malcom, E.W. (1990) The Generation of Quinones from Lignin and Lignin-Related Compounds, Diels-Adler Reactions of Lignin-Derived Quinones, Lignin-Derived Quinones as Pulping Additives. Institute of Paper Science and Technology Paper Series No. 349, 1-57.
[13]
Cedeno, D. and Bozell, J.J. (2012) Catalytic Oxidation of Para-Substituted Phenols with Cobalt-Schiff Base Complexes/O2—Selective Conversion of Syringyl and Guaiacyl Lignin Models to Benzoquinones. Tetrahedron Letters, 53, 2380-2383. http://dx.doi.org/10.1016/j.tetlet.2012.02.093
[14]
Canevali, C., Orlandi, M., Pardi, L., Rindone, B., Scotti, R., Sipila, J. and Morazzone, F. (2002) Oxidative Degradation of Monomeric and Dimeric Phenylpropanoids: Reactivity and Mechanistic Investigation. Journal of the Chemical Society, Dalton Transactions, No. 15, 3007-3014. http://dx.doi.org/10.1039/b203386k
[15]
Biannic, B. and Bozell, J.J. (2013) Efficient Cobalt-Catalyzed Oxidative Conversion of Lignin Models to Benzoquinones. Organic Letters, 15, 2730-2733. http://dx.doi.org/10.1021/ol401065r
[16]
Schmidt, R., Stocker, M., Akporiaye, D., Torstad, E.H. and Olsen, A. (1995) High-Resolution Electron Microscopy and X-Ray Diffraction Studies of MCM-48. Microporous Materials, 5, 1-7.
http://dx.doi.org/10.1016/0927-6513(95)00030-D
[17]
Sadual, R. (2015) Oxidation of Lignin Model Phenolic Monomer over Cobalt Containing Solid Catalysts. PhD Thesis, North Orissa University, Baripada.
[18]
Flanigen, E.M., Khatami, H. and Szymanski, H.A. (1971) Infrared Structural Studies of Zeolite Frameworks. In: Flanigen, E.M. and Sand, L.B., Ed., Molecular Sieve Zeolites, Advances in Chemistry 101, American Chemical Society, Washington DC, 201-229. http://dx.doi.org/10.1021/ba-1971-0102
[19]
Chen, J.S., Li, Q.H., Xu, R.R. and Xiao, F.S. (1995) Distinguishing the Silanol Groups in the Mesoporous Molecular Sieve MCM-41. Angewandte Chemie International Edition in English, 34, 2694-2696.
http://dx.doi.org/10.1002/anie.199526941
[20]
Zhao, X.S., Lu, G.Q., Whittaker, A.K., Millar, G.J. and Zhu, H.Y. (1997) Comprehensive Study of Surface Chemistry of MCM-41 Using 29Si CP/MAS NMR, FTIR, Pyridine-TPD, and TGA. The Journal of Physical Chemistry B, 101, 6525-6531. http://dx.doi.org/10.1021/jp971366+
[21]
Crestini, C., Pastoni, A. and Taguatesta, P. (2004) Metalloporphyrins Immobilized on Motmorillonite as Biomimetic Catalysts in The Oxidation of Lignin Model Compounds. Journal of Molecular Catalysis A: Chemical, 208, 195-202.
http://dx.doi.org/10.1016/j.molcata.2003.07.015
[22]
Sadual, R., Badamali, S.K. and Singh, R.K. (2014) Studies on Mesoporous CoSBA-15 Catalysed Selective Oxidation of a Lignin Model Phenolic Monomer. Advanced Porous Materials, 2, 48-53. http://dx.doi.org/10.1166/apm.2014.1044
