Summary
Nitroarenes can be reduced in high yields to the corresponding anilines by transfer hydrogenation using a stable H-donor, polymer-supported formate (PSF) in combination with palladium acetate (catalytic). The reactions occur at 100–120∘C in dimethyl-formamide and the PSF can be recycled for at least three runs. The procedure is chemoselective for nitro group; ester, ketone, aldehyde, and halide substituents on aromatic ring remain unaffected.
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References
Larock, R.C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, Wiley-VCH, New York, 1999, pp. 823–827.
Sandler, S.R. and Karo, W., Organic Functional Group Preparation, Academic Press, New York, 1968, pp. 339–345.
Kabalka, G.W. and Verma, R.S., Reduction of nitro and nitroso compounds, In Trost, B.M. and Fleming, E. (Eds.) Comprehensive Organic Synthesis, Vol. 8, Pergamon Press, Oxford, 1991, pp. 363–379.
Hudlicky, M., Reductions in Organic Chemistry, American Chemical Society, Washington DC, 1996.
Lewis, P.A. (Ed.), Pigment Handbook, Wiley, New York, 1988; Vol 1.
Negwer, M., Organic-Chemical Drugs and Their Synonyms (An International Survey); 7th Ed., Akademie Verlag GmbH, Berlin, 1994.
Montogomery, J.H., Agrochemicals Desk Reference: Environmental Data, Lewis Publishers, Chelsea, MI, 1993.
D'Aproano, G., Schiavon, G., Zotti, G. and Leclere, M., Synthesis and characterization of polyaniline derivatives: Poly(2-alkoxyanilines) and poly(2,5-dialkoxyanilines), Chem. Mater., 7 (1995) 33– 42.
Solomons, T.W.G., Organic Chemistry, 6th Ed., Wiley, New York, 1996, pp. 925–932.
Rylander, P., Catalytic Hydrogenation in Organic Synthesis, Academic Press, New York, 1979.
Ono, N., The Nitro Group in Organic Synthesis, Wiley-VCH, New York, 2001, pp. 170–172.
Hartman, W.W., Dickey, J.B. and Stampfli, J.G., 2,6-Dibromoquinone-4-chloroimide, Org. Synth., 2 (1943) 175–177.
Fox, B.A. and Threlfall, T.L., 2,6-Diaminopyridine, Org. Synth., 5 (1973) 346–351.
Wertheim, E., Orthanilic acid, Org. Synth., 2 (1943) 471–473.
Moody, C.J. and Pitts, M.R., Indium as a reducing agent: Reduction of aromatic nitro groups, Synlett, (1998) 1028.
Banik, B.K., Mukhopadhyay, C., Venkattaman, M.S. and Becker, F.F., A facile reduction of aromatic nitro compounds to aromatic amines by samarium and iodine, Tetrahedron Lett., 39 (1998) 7243–7246.
Basu, M.K., Becker, F.F. and Banik, B.K., Ultrasound-promoted highly efficient reduction of aromatic nitro compounds to the aromatic amines by samarium/ammonium chloride, Tetrahedron Lett., 41 (2000) 5603–5606.
Braude, E.A. and Linstead, R.P., Hydrogen transfer. Part I. Introductory survey, J. Chem. Soc., (1954) 3544–3547.
Brieger, G. and Nestrick, T.J., Catalytic transfer hydrogenation, Chem. Rev., 74 (1974) 567–580.
Johnstone, R.A.W., Wilby, A.H. and Entwistle, I.D., Homogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds, Chem. Rev., 85 (1985) 129– 170.
Gowda, B., Mahesh, B. and Shankare, G., Zinc-Catalyzed Ammonium Formate Reductions: Reduction of Nitro Compounds, Ind. J. Chem. Sect. B, 40 (2001) 75–77 and references cited therein.
Bhaumik, K. and Akamanchi, K.G., Nitroarene reduction using Raney nickel alloy with ammonium chloride in water, Can. J. Chem., 81 (2003) 197–198.
Ram, S. and Ehrenkaufer, R.E., Ammonium formate in organic Synthesis: A versatile agent in catalytic hydrogen transfer reductions. Synthesis, (1988) 91–95.
Pratap, T.V. and Baskaran, S., Direct conversion of aryl nitro compounds to formanilides under catalytic transfer hydrogenation conditions, Tetrahedron Lett., 42 (2001) 1983–1985.
Obrecht, D. and Villalgordo, J.M., Solid-Supported Combinatorial and Parallel Synthesis of Small Molecular-Weight Compound Libraries, Pergamon, Oxford, 1998.
Terrett, N.K., Combinatorial Chemistry, Oxford University Press, Oxford, 1998.
Brown, A.R., Hermkenes, P.H.H., Ottenheijm, H.C.J. and Rees, D.C., Solid phase synthesis, Synlett, (1998) 817–827.
Kirschning, A., Monenschein, H. and Wittenberg, R., Functionalized polymers–emerging versatile tools for solution-phase chemistry and automated parallel synthesis, Angew. Chem. Int. Ed. Engl., 40 (2001) 650–679 and references cited therein.
Zaragoza Dorwald, F., Organic Synthesis on Solid Support, Wiley-VCH, Weinheim, 2000.
Kirschning, A., Borohydride Exchange Resins (BER) —a Group of versatile and powerful polymer-supported reductants, J. Prakt. Chem., 342 (2000) 508–511.
Basu, B., Bhuiyan, M.M.H. and Jha, S., Palladium mediated chemoselective reduction of α,β-unsaturated cyano esters with potassium formate, Synth. Commun., 33 (2003) 291–296.
Basu, B., Jha, S., Bhuiyan, M.M.H. and Das, P., A simple protocol for direct reductive amination of aldehydes and ketones using potassium formate and catalytic palladium acetate, Synlett, (2003) 555–557.
Basu, B., Bhuiyan, M.M.H., Das, P. and Hossain, I., Catalytic transfer reduction of conjugated alkenes and an imine using polymer-supported formates, Tetrahedron Lett., 44 (2003) 8931–8934.
Banik, B.K., Barakat, K.J., Wagle, D.R., Manhas, M.S. and Bose, A.K., Microwave-assisted rapid and simplified hydrogenation, J. Org. Chem., 64 (1999) 5746–5753.
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Basu, B., Das, P. & Das, S. Transfer hydrogenation using recyclable polymer-supported formate (PSF): Efficient and chemoselective reduction of nitroarenes. Mol Divers 9, 259–262 (2005). https://doi.org/10.1007/s11030-005-8106-1
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DOI: https://doi.org/10.1007/s11030-005-8106-1
Key Words
- aniline
- ion-exchange resin
- nitroarene
- palladium acetate
- polymer-supported formate
- transfer hydrogenation