Abstract
In situ 13C MAS NMR spectroscopy under continuous-flow (CF) conditions was applied to study the mechanism of the methylation of phenol by methanol on acidic zeolite H–Y. Ex situ GC-MS was used as a complementary technique to confirm the nature of the chemical species remaining on the catalyst after the in situ MAS NMR investigations. Anisole and cresols were observed as the main reaction products in the initial step of the reaction. By use of the stopped-flow (SF) technique, the consecutive transformation of anisole to cresols was observed at the reaction temperature of 413K indicating that anisole is an unstable primary product and an important intermediate.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
(a)J.F. Haw, In-situ Spectroscopy in Heterogeneous Catalysis (Wiley-VcH, Weinheim, 2002) p. 276;(b) B.M. Weckhuysen, Chem. Commun. (2002) 97; (c) M. Hunger and J. Weitkamp, Angew. Chem. Int. Ed. 40 (2001) 2954; (d) X. Han, Z. Yan, W. Zhang and X. Bao, Curr. Org. Chem. 5 (2001) 1017; (e) E.G. Derouane, H.Y. He, H.S.B. Derouane-Abd and I.I. Ivanova, Catal. Lett. 58 (1999) 1; (f) A. Brueckner, Catal. Rev.-Sci. Eng. 45 (2003) 97–150.
(a)M. Hunger and T. Horvath, J. Chem. Soc., Chem Commun. (1995) 1423;(b) M. Hunger, M. Seiler and T. Horvath, Catal. Lett. 57 (1999) 199; (c) M. Seiler, U. Schenk and M. Hunger, Catal. Lett. 62 (1999) 139; (d) M. Hunger, M. Seiler and A. Buchholz, Catal. Lett. 74 (2001) 61; (e) M. Seiler, W. Wang, A. Buchholz and M. Hunger, Catal. Lett. 88 (2003) 187.
W. Wang, M. Seiler, I.I. Ivanova, U. Sternberg, J. Weitkamp and M. Hunger, J. Am. Chem. Soc. 124 (2002) 7548.
W. Wang, M. Seiler, I.I. Ivanova, J. Weitkamp and M. Hunger, Chem. Commun. (2001) 1362.
W. Wang, M. Seiler and M. Hunger, J. Phys. Chem. B 105 (2001) 12553.
W. Wang, A. Buchholz, A. Arnold, M. Xu and M. Hunger, Chem. Phys. Lett. 370 (2003) 88.
W. Wang, A. Buchholz, M. Seiler and M. Hunger, J. Am. Chem. Soc. 125 (2003) 15260.
S. Balsama, P. Beltrame, P.L. Beltrame, P. Carniti, L. Forni and G. Zuretti, Appl. Catal. 13 (1984) 161.
J. Xu, A.Z. Yan and Q.H. Xu, React. Kinet. Catal. Lett. 62 (1997) 71.
R.F. Parton, J.M. Jacobs, D.R. Huybrechts and P.A. Jacobs, in: Zeolites as Catalysts, Sorbents and Detergent Builders, Stud. Surf. Sci. Catal., Vol. 46 eds. H.G. Karge and J. Weitkamp (Elsevier>, Amsterdam, 1989) p. 163.
M. Renaud, P.D. Chantal and S. Kaliaguine, Can. J. Chem. Eng. 64 (1986) 787.
L. Garcia, G. Giannetto, M.R. Goldwasser, M. Guisnet and P. Magnoux, Catal. Lett. 37 (1996) 121.
Y. Ojeda, M.R. Goldwasser and M. Torrealba, in: Catalysis of Organic Reactions, eds. M.G. Skaros and M.L. Prunier (Marcel Dekker, New York, Basel, 1994)p. 535.
M. Marczewski, J.P. Bodibo, G. Perot and M. Guisnet, J. Mol. Catal. 50 (1989) 211.
E. Santacesaria, M.D. Serio, P. Ciambelli, D. Gelosa and S. Carra, Appl. Catal. 64 (1990) 101.
K.G. Bhattacharyya, A.K. Talukdar, P. Das and S. Sivasanker, J. Mol. Catal. A: Chem. 197 (2003) 255.
M. Marczewski, G. Perot and M. Guisnet, in: Heterogeneous Catalysis and Fine Chemicals, Stud. Surf. Sci. Catal., Vol. 41, eds. M. Guisnetet al. (Elsevier, Amsterdam, 1988) p. 273.
M. Hunger and T. Horvath, Catal. Lett. 49 (1997) 95.
CRC Handbook of Chemistry and Physics, 53rd ed., (The Chemical Rubber Company, Ohio, 1972) p. C-421.
CRC Handbook of Chemistry and Physics, 53rd ed., (The Chemical Rubber Company, Ohio, 1972) p. D-158.
H. Kalinowski, S. Berger and S. Braun, 13 C-NMR-Spektroskopie (Georg Thieme Verlag, Stuttgart, New York, 1984) p. 155.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wang, W., De Cola, P.L., Glaeser, R. et al. Methylation of Phenol by Methanol on Acidic Zeolite H–Y Investigated by in situ CF MAS NMR Spectroscopy. Catalysis Letters 94, 119–123 (2004). https://doi.org/10.1023/B:CATL.0000019341.67169.ac
Issue Date:
DOI: https://doi.org/10.1023/B:CATL.0000019341.67169.ac