Skip to content
Publicly Available Published by De Gruyter February 3, 2012

Replacing benzyl chloride with benzyl alcohol in heterogeneous catalytic benzylation of aromatic compounds

  • Natalia Candu , Stefan Wuttke , Erhard Kemnitz , Simona M. Coman and Vasile I. Pârvulescu

Comparative catalytic liquid-phase benzylation of aromatic compouds (e.g., benzene and ethylbenzene) to diphenylmethane (DPM) derivatives with benzyl alcohol (BnOH) was investigated over various catalysts like zeolite (HSZ 600 mordenite, CBV 20A mordenite, H-beta zeolites with Si/Al ratios of 10.8 and 35.8, respectively) and nano-structured inorganic fluorides (MgF2) at 80–120 °C under atmospheric pressure. The reactions were carried out in batch reactors using two methodologies: (i) by introducing both the solution of substrate and BnOH at the beginning of the reaction, and (ii) by drop-wise addition of BnOH (1–2 drops/min for 4 h) to the reaction mixture. The analysis of the reaction products indicated that the conversion and product distribution depend on the experimental method and the nature of the catalyst. The reaction rate was found to correlate to the nucleophilicity of the substrates and their ability to delocalize the positive charge in the Wheland intermediate by inductive and resonance effects.


1 10.1351/pac200072071233, R. A. Sheldon. Pure Appl. Chem.72, 1233 (2000).Search in Google Scholar

2 T. W. Bastock, J. H. Clark. In Speciality Chemicals, Elsevier, London (1991).Search in Google Scholar

3 10.1002/(SICI)1097-4660(199803)71:3<209::AID-JCTB786>3.0.CO;2-Z, B. M. Khadilkar, S. D. Borkar. Chem. Technol. Biotechnol.71, 209 (1998).Search in Google Scholar

4 D. Yin, C. Li, L. Tao, N. Yu, S. Hu, D. Yin. J. Mol. Catal., A245, 260 (2006).10.1016/j.molcata.2005.10.010Search in Google Scholar

5 G. A. Olah. In Friedel–Crafts Chemistry, John Wiley, New York (1973).Search in Google Scholar

6 M. C. Clark, C. M. Smith, D. L. Stern, J. S. Beck. In Handbook of Heterogeneous Catalysis, 2nd ed., G. Ertl, H. Knözinger, F. Schüth, J. Weitkamp (Eds.), Vol. 7, p. 3153, Wiley-VCH (2008).Search in Google Scholar

7 X. Hu, G. K. Chuah, S. Jaenicke. Appl. Catal., A217, 1 (2001).10.1016/S0926-860X(01)00574-9Search in Google Scholar

8 S. Sebti, R. Tahir, R. Nazih, S. Boulaajaj. Appl. Catal., A218, 25 (2001).10.1016/S0926-860X(01)00599-3Search in Google Scholar

9 M. Kurian, S. Sugunan. Indian J. Chem., Sect. A42, 2480 (2003).Search in Google Scholar

10 10.1002/chem.200801702, S. Wuttke, S. M. Coman, G. Scholz, H. Kirmse, A. Vimont, M. Daturi, S. L. M. Schroeder, E. Kemnitz. Chem.—Eur. J.14, 11488 (2008).Search in Google Scholar

11 10.1002/adsc.200800411, S. M. Coman, S. Wuttke, A. Vimont, M. Daturi, E. Kemnitz. Adv. Synth. Catal.350, 2517 (2008).Search in Google Scholar

12 10.1002/cctc.200900205, S. M. Coman, V. I. Parvulescu, S. Wuttke, E. Kemnitz. ChemCatChem2, 92 (2010).Search in Google Scholar

13 S. B. Troncea, S. Wuttke, E. Kemnitz, S. M. Coman, V. I. Parvulescu. Appl. Catal., B107, 260 (2011).10.1016/j.apcatb.2011.07.021Search in Google Scholar

14 10.1002/anie.201002090, A. Negoi, S. Wuttke, E. Kemnitz, D. Macovei, V. I. Parvulescu, C. M. Teodorescu, S. M. Coman. Angew. Chem., Int. Ed.49, 8134 (2010).Search in Google Scholar

15 10.1016/j.cattod.2009.10.008, S. Wuttke, S. M. Coman, J. Kröhnert, F. C. Jentoft, E. Kemnitz. Catal. Today152, 2 (2010).Search in Google Scholar

16 N. Candu, S. Wuttke, E. Kemnitz, S. M. Coman, V. I. Parvulescu. Appl. Catal., A391, 169 (2011).10.1016/j.apcata.2010.08.004Search in Google Scholar

17 N. Candu, M. Florea, S. M. Coman, V. I. Parvulescu. Appl. Catal., A393, 206 (2011).10.1016/j.apcata.2010.11.044Search in Google Scholar

18 10.1016/j.catcom.2004.02.013, V. D. Chaube. Catal. Commun.5, 321 (2004).Search in Google Scholar

19 10.1016/S0144-2449(97)00009-2, J. Datka, B. Gil, A. Kubacka. Zeolites18, 245 (1997).Search in Google Scholar

20 10.1039/b817572a, S. M. Coman, P. Patil, S. Wuttke, E. Kemnitz. Chem. Commun. 460 (2009).Search in Google Scholar

21 10.1016/0040-4039(93)85119-H, G. D. Yadav, T. S. Thorat, P. S. Khumbar. Tetrahedron Lett.34, 529 (1993).Search in Google Scholar

22 A. B. Deshpande, A. R. Bajpai, S. D. Samant. Appl. Catal., A209, 229 (2001).10.1016/S0926-860X(00)00777-8Search in Google Scholar

23 M. H. C. de la Cruz, J. F. C. da Silva, E. R. Lachter. Appl. Catal., A245, 377 (2003).10.1016/S0926-860X(02)00639-7Search in Google Scholar

Online erschienen: 2012-2-3
Erschienen im Druck: 2012-2-3

© 2013 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 21.9.2023 from
Scroll to top button