GSC  Vol.5 No.3 , August 2015
Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts
The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Cite this paper
Le, N. , Byun, A. , Han, Y. , Lee, K. and Kim, H. (2015) Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts. Green and Sustainable Chemistry, 5, 115-127. doi: 10.4236/gsc.2015.53015.
[1]   Wittcoff, H.A., Reuben, B.G. and Plotkin, J.S. (2004) Industrial Organic Chemicals. 2nd Edition, Wiley-Interscience, New York.

[2]   Hartwig, J.F. (2002) Handbook of Organo-Palladium Chemistry for Organic Synthesis. Vol. 1, Wiley-Interscience, New York, 1051.

[3]   Kreye, O., Mutlu, H. and Meier, M.A.R. (2013) Sustainable Routes to Polyurethane Precursors. Green Chemistry, 15, 1431-1455.

[4]   Roesky, P.W. (2009) Catalytic Hydroaminoalkylation. Angewandte Chemie International Edition, 48, 4892-4894.

[5]   Kruger, K., Tillack, A. and Beller, M. (2009) Recent Innovative Strategies for the Synthesis of Amines: From C-N Bond Formation to C-N Bond Activation. ChemSusChem, 2, 715-719.

[6]   Muller, T.E., Hultzsch, K.C., Yus, M., Foubelo, F. and Tada, M. (2008) Hydroamination: Direct Addition of Amines to Alkenes and Alkynes. Chemical Reviews, 108, 3795-3892.

[7]   Le, N.T., Lakshmanan, P., Cho, K., Han, Y. and Kim, H. (2013) Selective Oxidation of 5-Hydroxymethyl-2-Furfural into 2,5-Diformylfuran over VO2+ and Cu2+ Ions Immobilizedon Sulfonated Carbon Catalysts. Applied Catalysis A: General, 464-465, 305-312.

[8]   Yang, Z.Z., Deng, J., Pan, T., Guo, Q.X. and Fu, Y. (2012) A One-Pot Approach for Conversion of Fructose to 2,5- Diformylfuran by Combination of Fe3O4-SBA-SO3H and K-OMS-2. Green Chemistry, 14, 2986-2989.

[9]   Takagaki, A., Takahashi, M., Nishimura, S. and Ebitani, K. (2011) One-Pot Synthesis of 2,5-Diformylfuran from Carbohydrate Derivatives by Sulfonated Resin and Hydrotalcite-Supported Ruthenium Catalysts. ACS Catalysis, 1, 1562- 1565.

[10]   Ma, J., Du, Z., Xu, J., Chu, Q. and Pang, Y. (2011) Efficient Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5- Diformylfuran, and Synthesis of a Fluorescent Material. ChemSusChem, 4, 51-54.

[11]   Gandini, A. and Belgacem, M.N. (1997) Furans in Polymer Chemistry. Progress in Polymer Science, 22, 1203-1379.

[12]   Moreau, C., Belgacem, M.N. and Gandini, A. (2004) Recent Catalytic Advances in the Chemistry of Substituted Furans from Carbohydrates and in the Ensuing Polymers. Topics in Catalysis, 27, 11-30.

[13]   Lichtenthaler, F.W. (2002) Unsaturated O- and N-Heterocycles from Carbohydrate Feedstocks. Accounts of Chemical Research, 35, 728-737.

[14]   Molitor, E.J. and Toyzan, T.W. (2008) Process for the Reductive Amination of Aldehydes and Ketones. WO Patent No. 076795A1.

[15]   Kampmann, D., Weber, J. and Kniep, C. (1991) Process for the Preparation of Diamines. US Patent No. 5055618.

[16]   Nagareda, K., Tokuda, Y. and Suzuki, S. (1998) Process for Producing Diamines from Dialdehydes. European Patent No. 0878462A1.

[17]   Tokuda, Y. and Suzuki, S. (2003) Process for Producing Diamines from Dialdehydes. European Patent No. 1348688A1.

[18]   Haas, T., Tacke, T., Pfeffer, J.C., Klasovky, F., Rimbach, M., Volland, M. and Ortelt, M. (2012) Process for Producing 2,5-Diformylfuran and Derivatives thereof. WO Patent No. 004069A1.

[19]   Devred, F., Hoffer, B.W., Sloof, W.G., Kooyman, P.J., van Langeveld, A.D. and Zandbergen, H.W. (2003) The Genesis of the Active Phase in Raney-Type Catalysts: The Role of Leaching Parameters. Applied Catalysis A: General, 244, 291-300.

[20]   Fouilloux, P. (1983) The Nature of Raney Nickel, Its Adsorbed Hydrogen and Its Catalytic Activity for Hydrogenation Reactions (Review). Applied Catalysis, 8, 1-42.

[21]   Zhang, L., Lu, Q., Hou, Y. and Ying, W. (2013) Synthesis of an Amine Terminated Polyether: Effects of the Activation Conditions on a Raney Nickel Catalyst. Reaction Kinetics Mechanism and Catalysis, 108, 139-149.

[22]   Biesinger, M.C., Payne, B.P., Grosvenor, A.P., Lau, L.W.M., Gerson, A.R. and Smart, R.S.C. (2011) Resolving Surface Chemical States in XPS Analysis of First Row Transition Metals, Oxides and Hydroxides: Cr, Mn, Fe, Co and Ni. Applied Surface Science, 257, 2717-2730.

[23]   Moulder, J.F., Stickle, W.F., Sobol, P.E. and Bomben, K.D. (1995) Handbook of X-Ray Photoelectron Spectroscopy. Physical Electronics Inc., Chanhassen.

[24]   Biesinger, M.C., Payne, B.P., Lau, L.W.M., Gerson, A. and Smart, R.S.C. (2009) X-Ray Photoelectron Spectroscopic Chemical State Quantification of Mixed Nickel Metal, Oxide and Hydroxide Systems. Surface and Interface Analysis, 41, 324-332.

[25]   Gomez, S., Peters, J.A. and Maschmeyer, T. (2002) The Reductive Amination of Aldehydes and Ketonesand the Hydrogenation of Nitriles: Mechanistic Aspects and Selectivity Control. Advanced Synthesis and Catalysis, 344, 1037- 1057.

[26]   Qi, F., Hu, L., Lu, S., Cao, X. and Gu, H. (2012) Selective Synthesis of Secondary Amines by Pt Nanowire Catalyzed Reductive Amination of Aldehydes and Ketones with Ammonia. Chemical Communication, 48, 9631-9633.

[27]   Gomez, S., Peters, J.A., van der Waal, J.C., van den Brink, P.J. and Maschmeyer, T. (2004) The Rationalization of Catalyst Behavior in the Reductive Amination of Benzaldehyde with Ammonia Using a Simple Computer Model. Applied Catalysis A: General, 261, 119-125.

[28]   Bagal, D.B., Watile, R.A., Khedkar, M.V., Dhake, K.P. and Bhanage, B.M. (2012) PS-Pd-NHC: An Efficient and Heterogeneous Recyclable Catalyst for Direct Reductive Amination of Carbonyl Compounds with Primary/Secondary Amines in Aqueous Medium. Catalysis Science and Technology, 2, 354-358.