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Journal of Materials Science

, Volume 44, Issue 24, pp 6741–6746 | Cite as

Gas-phase Beckmann rearrangement of cyclododecanone oxime on Al,B-MCM-41 mesoporous materials

  • Tomas David Conesa
  • Rafael Luque
  • Juan Manuel Campelo
  • Diego Luna
  • Jose Maria Marinas
  • Antonio Angel Romero
Mesostructured Materials

Abstract

Gas-phase Beckmann rearrangement of cyclododecanone oxime (Cdox) to ω-laurolactam is reported for the first time on Al,B-MCM-41 catalysts. The Cdox conversion was studied by using a temperature programmed reaction experiment in the 325–450 °C temperature range employing 0.15 M Cdox in toluene/acetone solution. The oxime conversion increased gradually with reaction temperature from ca. 90% at 325 °C to ca. 95% at 450 °C, whereas the yield of the desired product ω-laurolactam decreased. The optimal reaction temperature was 375 °C, which balanced the conversion of Cdox, selectivity to ω-laurolactam and catalyst lifetime. In parallel, liquid-phase experiments were carried out under conventional heating. Weak and medium strength acid sites, higher strong acid B/L ratios and adequate pore diameter of untreated Al,B-MCM-41 materials favored an optimal performance for the gas-phase Beckmann rearrangement of Cdox, clearly improving the conversion, selectivity to ω-laurolactam and catalyst lifetime in gas-phase with respect to the conventional liquid-phase reactions.

Keywords

Oxime Chlorobenzene Aldol Reaction Beta75 Zeolite Beckmann Rearrangement 

Notes

Acknowledgements

This research was subsidized by Grants from the Dirección General de Investigación (Projects CTQ2007-65754/PPQ, CTQ2008-01330), Ministerio de Ciencia y Tecnología, FEDER funds, and from the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Project P07-FQM-2695).

References

  1. 1.
    United Nations Environment Programme Publications. https://doi.org/www.chem.unep.ch/irptc/sids/OECDSIDS/947046.pdf
  2. 2.
    Forni L, Fornasari G, Giordano G, Lucarelli C, Katovic A, Trifiro F, Perri C, Nagy JB (2004) Phys Chem Chem Phys 6:1842CrossRefGoogle Scholar
  3. 3.
    Mao D, Chen Q, Lu G (2003) Appl Catal A 244:273CrossRefGoogle Scholar
  4. 4.
    Maheswari R, Shanthi K, Sivakumar T, Narayanan S (2003) Appl Catal A 248:291CrossRefGoogle Scholar
  5. 5.
    Conesa TD, Campelo JM, Luna D, Marinas JM, Romero AA (2007) Appl Catal B 70:567CrossRefGoogle Scholar
  6. 6.
    Misono M, Inui T (1999) Catal Today 51:369CrossRefGoogle Scholar
  7. 7.
    Tsuji H, Setoyama T (2005) Chem Lett 34:1232CrossRefGoogle Scholar
  8. 8.
    Ushikubo T (2000) Catal Today 57:331CrossRefGoogle Scholar
  9. 9.
    Forni L, Fornasari G, Tosi C, Trifiro F, Vaccari A, Dumeignil F, Grimblot J (2003) Appl Catal A 248:47CrossRefGoogle Scholar
  10. 10.
    Corma A, Iborra S, Rodríguez MI (2004) WO Patent 2004037785 A1Google Scholar
  11. 11.
    Conesa TD, Mokaya R, Yang Z, Luque R, Campelo JM, Romero AA (2007) J Catal 252:1 and references thereinGoogle Scholar
  12. 12.
    Michel JC, Potin P (1980) US Patent 4 211 700Google Scholar
  13. 13.
    Kuroda N, Kawai J, Shimomura H (2003) EP Patent 1 329 448 A1Google Scholar
  14. 14.
    García L, Del Pino M (1994) ES Patent 2 048 098Google Scholar
  15. 15.
    Ollivier J (1998) US Patent 5 719 316Google Scholar
  16. 16.
    Ollivier J, Drutel D (1999) WO Patent 9 901 424Google Scholar
  17. 17.
    Ollivier J (1997) EP Patent 0 798 290 A1Google Scholar
  18. 18.
    Hans M, Heinz-Werner V (1987) US Patent 4 689 412Google Scholar
  19. 19.
    Camblor MA, Corma A, García H, Semmer-Herléndan V, Valencia S (1998) J Catal 177:267CrossRefGoogle Scholar
  20. 20.
    Yamamoto S, Haruta A, Fukuda Y (2005) JP Patent 2005022977Google Scholar
  21. 21.
    Yamamoto S, Haruta A, Fukuda Y (2005) JP Patent 2005023014Google Scholar
  22. 22.
    Corma A (1997) Chem Rev 97:2373CrossRefGoogle Scholar
  23. 23.
    Gonzalez-Arellano C, Corma A, Iglesias M, Sanchez F (2004) Adv Synth Catal 346:1316CrossRefGoogle Scholar
  24. 24.
    Bhattacharyya S, Lelong G, Saboungi ML (2006) J Exp Nanosci 1:375CrossRefGoogle Scholar
  25. 25.
    Gonzalez-Arellano C, Corma A, Iglesias M, Sanchez F (2008) Eur J Org Chem 1107Google Scholar
  26. 26.
    Campelo JM, Conesa TD, Luna D, Marinas JM, Romero AA (2005) Stud Surf Sci Catal 158:1421CrossRefGoogle Scholar
  27. 27.
    Conesa TD, Hidalgo JM, Luque R, Campelo JM, Romero AA (2006) Appl Catal A 299:224CrossRefGoogle Scholar
  28. 28.
    Rozwadowski M, Lezanska M, Wloch J, Erdmann K, Golembiewski R, Kornatowski J (2001) Chem Mater 13:1609CrossRefGoogle Scholar
  29. 29.
    Praserthdam P, Isarangura na Ayutthaya S (2004) Catal Today 97:137CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2009

Authors and Affiliations

  • Tomas David Conesa
    • 1
  • Rafael Luque
    • 1
  • Juan Manuel Campelo
    • 1
  • Diego Luna
    • 1
  • Jose Maria Marinas
    • 1
  • Antonio Angel Romero
    • 1
  1. 1.Departamento de Química Orgánica, Facultad de CienciasUniversidad de CórdobaCórdobaSpain

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