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The effect of the components of the PdCl2/Fe/I2/Py catalytic system on nitrobenzene carbonylation to ethyl N-phenylcarbamate

  • Published:
Central European Journal of Chemistry

Abstract

The PdCl2/Fe/I2/Py catalytic system (Py-pyridine), reported to be highly active in the reaction of nitrobenzene carbonylation to ethyl phenylcarbamate was studied. The present paper describes the role of catalyst components and its effect on the activity and selectivity of the catalyst. The increase in the amount of PdCl2 in the system while retaining a constant level of the other catalyst components, results in the increase of both carbamate and aniline yields. The increase in the amount of iron while retaining the other components constant, initially causes an increase in the carbamate yield; however, at Fe: Pd ratios higher than 36, the carbamate yield remains constant. The change in the amount of iron has no effect on the amount of aniline formed in the system. An increase in the amount of iodine in the system while retaining the other components constant, results in a decrease in carbamate yield and a considerable increase in the aniline yield of the reaction products.

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References

  1. S. Cenini, M. Pizzotti and C. Crotti: „Metal catalysed deoxygenation reactions by carbon monoxide of nitroso and nitro compounds”, Aspects of Homogeneous Catalysis, Vol. 6, (1988), pp. 97–198.

    CAS  Google Scholar 

  2. F. Ragaini and S. Cenini: “Mechanistic studies of palladium-catalysed carbonylation reaction of nitro compounds to isocyanates, carbamates and ureas”, J. Mol. Catal. A: Chem., Vol. 109, (1996), pp. 1–25.

    Article  CAS  Google Scholar 

  3. F. Paul: “Catalytic synthesis of isocyanates or carbamates from nitroaromatics using Group VIII transition metal catalysts”, Coord. Chem. Rev., Vol. 203, (2000), pp. 269–323.

    Article  CAS  Google Scholar 

  4. S.M. Islam, D. Mal, B.K. Palit and C.R. Saha: “Reductive carbonylation of nitroaromatics using RhA(CO)2”, J. Mol. Catal. A: Chem., Vol. 142, (1999), pp. 169–181.

    Article  CAS  Google Scholar 

  5. T. Mizuno and H. Alper: “Reductive carbonylation of nitrobenzenes catalyzed by a new binuclear rhodium complex”, J. Mol. Catal. A: Chem., Vol. 121, (1997), pp. 119–122.

    Article  CAS  Google Scholar 

  6. F. Ragaini and S. Cenini: “Mechanistic study of the Ru3(CO)12/chloride catalyzed carbonylation reactions of nitroarenes to carbamates and ureas; the role of the alkylammonium cation”, J. Mol. Catal. A: Chem., Vol. 161, (2000), pp. 31–38.

    Article  CAS  Google Scholar 

  7. S.J. Skoog and W.L. Gladfelter: “Activation of nitroarenes in the homogenous catalytic carbonylation of nitroaromatics via an oxygen-atom-transfer mechanism induced by inner-sphere electron transfer”, J. Amer. Chem. Soc., Vol. 119, (1997), pp. 11049–11060.

    Article  CAS  Google Scholar 

  8. S.B. Halligudi, N.H. Khan, R.I. Kureshy, E. Suresh and K. Venkatsubramanian: “Synthesis, structural characterization and catalytic carbonylation of nitrobenzene to phenylurethane using palladium(II) 1,10-phenanthroline diacetato complex”, J. Mol. Catal. A: Chem., Vol. 124, (1997), pp. 147–154.

    Article  CAS  Google Scholar 

  9. P. Wehman, H.M.A. van Donge, A. Hagos, P.C.J. Kamer and P.W.N.M. van Leeuwen: “Influence of various P/N and P/P ligands on the palladium-catalysed reductive carbonylation of nitrobenzene”, J. Organomet. Chem., Vol. 535, (1997), pp. 183–193.

    Article  CAS  Google Scholar 

  10. R. Santi, A.M. Romano, F. Panella and C. Santini: “Palladium and silver reductive catalyzed carbonylation of nitrobenzene to methyl N-phenylcarbamate”, J. Mol. Catal. A: Chem., Vol. 127, (1997), pp. 95–99.

    Article  CAS  Google Scholar 

  11. J. Mei, Y. Yang, Y. Xue and S. Lu: “Selective formation of unsymmetric ureas by selenium-catalyzed oxidative-reductive carbonylation with CO”, J. Mol. Catal. A: Chem., Vol. 191, (2003), pp. 135–139.

    Article  CAS  Google Scholar 

  12. V. Macho, M. Kralik, J. Hudec and J. Cingelova: “One stage preparation of Schiff’s bases from nitroarenes, aldehydes and carbon monoxide at presence of water”, J. Mol. Catal. A: Chem., Vol. 209, (2004), pp. 69–73.

    Article  CAS  Google Scholar 

  13. V. Macho, M. kralik and F. Halmo: “New catalytic system of N,N′-diphenylurea synthesis from nitrobenzene, carbon monoxide and water or aniline”, J. Mol. Catal. A: Chem., Vol. 109, (1996), pp. 119–125.

    Article  CAS  Google Scholar 

  14. J. Skupinska and M. Karpinska: “Nitrobenzene carbonylation in the presence of PdCl2/Fe/I2 and PdCl2Py2/Fe/I2 systems”, J. Mol. Catal. A: Chem., Vol. 161, (2000), pp. 69–73.

    Article  CAS  Google Scholar 

  15. J. Skupińska and M. Karpińska: “Nitrobenzene Transformations in the Carbonylation Reaction in the Presence of the PdCl2/Fe/I2/Py Catalyst System”, Appl. Catal., Vol. 267, (2004), pp. 59–66.

    Article  Google Scholar 

  16. J. Skupińska, M. Karpińska and M. Ołówek: “The nitrobenzene activation in the carbonylation over PdCl2/Fe/I2/Py catalytic system”, submitted for publication.

  17. J. Skupińska, M. Karpińska, L. Wachowski and M. Hofman: “Reductive carbonylation of nitrobenzene over Pd/Fe/I2/Py and Pd/C/Fe/I2/Py catalytic systems”, React. Kinet. Catal. Lett., Vol. 82, (2004), pp. 311–316.

    Article  Google Scholar 

  18. Gmelins Handbuch der Anorganischen Chemie, Vol. 59 Fe, Springer-Verlag, New York, 1979, p. 337.

  19. M. Aresta, P. Giannocaro, I. Tommasi, A. Dibenedetto, A.M.M. Lanfredi and F. Ugozzoli: “Synthesis and solid state and solution characterization of mono- and di-(η 1-C) carbamoyl-palladium complexes. New efficient palladium-catalyzed routes to carbamoyl chlorides: Key intermediates to isocyanates, carbamic esters, and ureas”, Organometallics, Vol. 19, (2000), pp. 3879–3889.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Laboratory of Physicochemical Fundaments of Chemical Technology, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland

    Jadwiga Skupińska, Monika Karpińska, Maria Ołówek & Teresa Kasprzycka-Guttman

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  1. Jadwiga Skupińska
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  2. Monika Karpińska
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  3. Maria Ołówek
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  4. Teresa Kasprzycka-Guttman
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Skupińska, J., Karpińska, M., Ołówek, M. et al. The effect of the components of the PdCl2/Fe/I2/Py catalytic system on nitrobenzene carbonylation to ethyl N-phenylcarbamate. cent.eur.j.chem. 3, 28–39 (2005). https://doi.org/10.2478/BF02476235

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  • DOI: https://doi.org/10.2478/BF02476235

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