View PDF Version
 
DOI: 10.1039/A706356C (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1998, 94, 985-993

Spectroscopic and kinetic study of the alkylation of phenol with dimethyl carbonate over NaX zeolite

(Note: The full text of this document is currently only available in the PDF Version )

Tilman Beutel

Abstract

The interaction of phenol and dimethyl carbonate (DMC) with acid–base sites in zeolite NaX has been studied using FTIR, UV and mass spectroscopy. At room temperature, phenol is predominantly adsorbed by hydrogen bonding to basic oxygen atoms of NaX. At higher temperature, phenol is partially deprotonated over basic sites to form phenolate anions; the latter undergo H-bonding to zeolitic hydroxy groups and Na+ ions. DMC forms a chelating complex with Na+ ions at room temperature which decomposes at 150°C into dimethyl ether and CO2. FTIR experiments of coadsorbed reactants show that, in the presence of phenol, DMC is mainly bonded by its carbonyl oxygen to Lewis acid sites. The formation of anisole sets in at 150°C and proceeds presumably via nucleophilic attack at the methyl carbon of DMC by the oxygen atom of H-bonded phenol or phenolate. Kinetic measurements reveal that the reaction order is negative in phenol but positive in DMC pointing to site blocking by strongly adsorbed phenol.

References

  1. R. Dowbenko in: Kirk-Othmer, Encyclopedia of Chemical Technology, ed. J. I. Kroschwitz and M. Houl-Grant, Wiley, New York, 4th edn., vol. 2, 1992, p.106 Search PubMed.
  2. G. M. Singerman, US Pat. 4 312 636, 1982 Search PubMed.
  3. K. Tanabe and T. Nishizaki, Stud. Surf. Sci. Catal., 1989, 51, 225.
  4. E. G. M. C. Samolada, Z. Kiparissides and I. A. Vasalos, J. Catal., 1995, 152, 52 CrossRef CAS.
  5. R. F. Parton, J. M. Jacobs, D. R. Huybrechts and P. A. Jacobs, in: Zeolites as Catalysts, Sorbent and Detergent Builders, ed. H. G. Karge and J. Weitkamp, Elsevier, Amsterdam, 1989, p. 163 Search PubMed.
  6. V. Durgakumari, S. Narayanan and L. Guczi, Catal. Lett., 1990, 5, 377 CrossRef CAS.
  7. S. Namba, T. Yashima, Y. Itaba and N. Hara, in Catalysis by Zeolites, ed. B. Imelik, C. Naccache, Y. Ben Taarit, J. C. Vedrine, G. Coudurier and H. Praliaud, Elsevier, Amsterdam, 1980, p. 105 Search PubMed.
  8. P. R. Hari Prasad Roa, P. Massiani and D. Barthomeuf, Catal. Lett., 1995, 31, 115 CrossRef CAS.
  9. Z.-H. Fu and Y. Ono, Catal. Lett., 1993, 21, 43 CAS.
  10. Y. Ono, Catal. Today, 1997, 35, 15 CrossRef CAS.
  11. I. Yu. Ponomarenko, E. A. Paukshtis and L. M. Koval, Russ. J. Phys. Chem., 1993, 67, 1549 Search PubMed.
  12. F. Hatayama, T. Ohno, T. Maruoka and H. Miyata, React. Kinet. Catal. Lett., 1991, 45, 265 CAS.
  13. L. Palmisano, M. Schiavello, A. Sclafani, G. Martra, E. Borello and S. Coluccia, Appl. Catal. B, 1994, 3, 117 CrossRef CAS.
  14. E. B. Wilson, Phys. Rev., 1934, 45, 706 CrossRef CAS.
  15. J. H. S. Green, J. Chem. Soc., 1961, 2236 RSC.
  16. R. Mecke, Z. Elektrochem., 1955, 59, 86 Search PubMed.
  17. J. David, J. Chem. Soc., 1954, 120 RSC.
  18. N. Mikami, Bull. Chem. Soc. Jpn., 1995, 68, 683 CAS.
  19. L. Doub and J. M. Vandenbelt, J. Am. Chem. Soc., 1947, 69, 2714 CrossRef CAS.
  20. F. A. Matsen, J. Am. Chem. Soc., 1950, 72, 5243 CrossRef CAS.
  21. A. Mukherjee, M. L. McGlashen and T. G. Spiro, J. Phys. Chem., 1995, 99, 4912 CrossRef CAS.
  22. M. I. Tejedor-Tejedor, E. C. Yost and M. A. Anderson, Langmuir, 1990, 6, 979 CrossRef CAS.
  23. J. S. Byrne, P. F. Jackson and K. J. Morgan, J. Chem. Soc., Perkin Trans. 2, 1975, 1800 Search PubMed.
  24. B. Collingwood, H. Lee and J. K. Wilmshurst, Aust. J. Chem., 1966, 19, 1637 CAS.
  25. Merck FT-IR Atlas, VCH, Weinheim, 1988 Search PubMed.
  26. L. Bertsch and H. W. Habgood, J. Phys. Chem., 1963, 67, 1621.
  27. M. L. Unland, J. Phys. Chem., 1978, 82, 580 CrossRef CAS.
  28. P. A. Jacobs, F. H. van Cauwelaert and E. F. Vansant, J. Chem. Soc., Faraday Trans., 1973, 2130 RSC.
  29. Compilation of Mass Spectral Data, ed. A. Cornu and R. Massot, Heyden, London, 1966 Search PubMed.
  30. Y. Matsamura, K. Hashimoto, H. Kobayashi and S. Yoshida, J. Chem. Soc., Faraday Trans., 1990, 86, 561 RSC.
  31. T. Ebata, T. Watanabe and N. Mikami, J. Phys. Chem., 1995, 99, 5761 CrossRef CAS.
  32. J. Datka and M. Boczar, React. Kinet. Catal. Lett., 1993, 51, 161 CAS.
  33. C. Binet, A. Jadi, J. Lamotte and J. C. Lavalley, J. Chem. Soc., Faraday Trans., 1996, 92, 123 RSC.
  34. M. O. Bulanin, B. N. Dolgov, T. A. Sperenskaya and N. P. Kharitonov, Zh. Fiz. Khim., 1957, 31, 1321 Search PubMed.
  35. M. Bensitel, V. Moravek, J. Lamotte, O. Saur and J. C. Lavalley, Spectrochim. Acta, Part A, 1987, 43, 1487.
  36. H. Knözinger, Angew. Chem., Int. Ed. Engl., 1968, 7, 791 CrossRef.
  37. S. M. McElvain, H. I. Anthes and S. H. Shapiro, J. Am. Chem. Soc., 1942, 64, 2525 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.