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Zeolitic behaviour of paratoluenesulfonic acid-modified clay in Friedel-Crafts synthesis of raspberry ketone

Published online by Cambridge University Press:  02 January 2018

M. Lakshmy ,
B.M. Chandrasekhar ,
B.S. Jai Prakash  and
Y.S. Bhat
M. Lakshmy
Affiliation:
Department of Chemistry, Bangalore Institute of Technology, K. R Road, Bangalore-560004, India
B.M. Chandrasekhar
Affiliation:
Department of Chemistry, Bangalore Institute of Technology, K. R Road, Bangalore-560004, India
B.S. Jai Prakash
Affiliation:
Department of Chemistry, Bangalore Institute of Technology, K. R Road, Bangalore-560004, India
Y.S. Bhat*
Affiliation:
Department of Chemistry, Bangalore Institute of Technology, K. R Road, Bangalore-560004, India
*
*E-mail: bhatys@yahoo.com
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Abstract

During solventless alkylation of phenol with 4-hydroxy-2-butanone under microwave irradiation, paratoluenesulfonic acid (pTSA)-modified montmorillonite clays gave, regioselectively, 4-(4′-hydroxyphenyl)-2-butanone (raspberry ketone). The duration for this reaction under microwave irradiation is much shorter than that of the conventional method. A comparative study of the alkylation reaction over a montmorillonite clay sample treated with 0.5 M-pTSA (0.5 M-pTSA clay) with that of Al-exchanged montmorillonite (Al3+-Mont) and beta-zeolite (HB) was carried out. The results show that the reaction time to reach equilibrium and the product distribution pattern for the reaction over 0.5 M-pTSA clay were similar to those values for the HB. Micropores formed on the clay surface during the pTSA treatment were found to enhance the rate of formation of C-alkylation. Micropores appear to enable better access to the active sites during the course of reaction.

Keywords

Friedel-Crafts alkylationraspberry ketonezeolitic behaviourparatoluenesulfonic acidmicropores
Type
Research Article
Information
Clay Minerals , Volume 50 , Issue 5 , December 2015 , pp. 573 - 581
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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References

A. G. Badische Anilin-und Soda-Fabri (1973) German Offen. Patent 2145308.Google Scholar
Arctander, S. (1969) Perfume and Flavour Chemicals (Aroma Chemicals), Vol. I. Montclair, New Jersey, USA.Google Scholar
Bunce, R.A. & Reeves, H.D. (1989) Amberlyst-15 catalyzed addition of phenols to α, β-unsaturated ketones. Synthetic Communications, 19, 1109–1117.Google Scholar
Chandrashekar, B.M., Jai Prakash, B.S. & Bhat, Y.S. (2011) Dealumination of zeolite BEA under microwave irradiation. ACS Catalysis, 1, 193–199.Google Scholar
Cheralathan, K.K., Kumar, I.S., Palanichamy, M. & Murugesan, V. (2003) Liquid phase alkylation of phenol with 4-hydroxybutan-2-one in the presence of modified zeolite HBEA. Applied Catalysis A: General, 241, 247–260.Google Scholar
Choudhary, T. & Misra, N.M. (2011) Role of clay as catalyst in Friedel—Craft alkylation. Bulletin of Materials Science, 34, 1273–1279.Google Scholar
Degnan, T.F. Jr., Smith, C.M. & Venkat, C.R. (2001) Alkylation of aromatics with ethylene and propylene: recent developments in commercial processes. Applied Catalysis A: General, 221, 283–294.CrossRefGoogle Scholar
Dutta, D.K. & Pathak, M.K. (2011) Process for the preparation of 4-(4-hydroxyphenyl)butan-2-one using solid acid clay catalyst. U.S. Patent 2011025743 A1.Google Scholar
Fukuda, Y., Nagano, M., Arimatsu, Y. & Futatsuka, M. (1998) In vitro studies on the depigmenting activity of 4-(p-hydroxyphenyl)-2-butanone. Journal of Occupational Health, 40, 137–142.Google Scholar
Hikima, T., Yokota, T., Ota, C., Hamada, K. & Sasaki, M. (2000) JP Patent 200095642.Google Scholar
Ikemoto, T., Nakatsugawa, H. & Yokota, T. (1998) JP Patent 10017462.Google Scholar
Korichi, S., Elias, A. & Mefti, A. (2009) Characterization of smectite after acid activation with microwave irradiation. Applied Clay Science, 42, 432—438.Google Scholar
Kokai Tokkyo Koho, Chisso Corporation, Japan, (1980) JP Patent 55151530.Google Scholar
Kosjek, B., Stampfer, W., Deursen, R.V., Faber, K. & Kroutil, W. (2003) Efficient production of raspberry ketone via ‘green’ biocatalytic oxidation. Tetrahedron, 59, 9517–9521.Google Scholar
Nagendrappa, G. (2011) Organic synthesis using clay and clay-supported catalysts. Applied Clay Science, 53, 106–138.Google Scholar
Namuangruk, S., Pantu, P. & Limtrakul, J. (2004) Alkylation of benzene with ethylene over faujasite zeolite investigated by the ONIOM method. Journal of Catalysis, 225, 523–530.Google Scholar
Poh, N.E., Nur, H., Muhid, M.N.M. & Hamdan, H. (2006) Sulphated AlMCM-41: mesoporous solid Brønsted acid catalyst for dibenzoylation of biphenyl. Catalysis Today, 114, 257–262.Google Scholar
Ramesh, S., Bhat, Y.S. & Jai Prakash, B.S. (2012) Microwave-activated pTSA dealuminated montmoril-lonite — a new material with improved catalytic activity. Clay Minerals, 47, 231–242.Google Scholar
Reddy, C.R., Vijayakumar, B., Iyengar, P., Nagendrappa, G. & Jai Prakash, B.S. (2004) Synthesis of phenylacetates using aluminium-exchanged montmorillonite clay catalyst. Journal of Molecular Catalysis A: Chemical, 223, 117–122.Google Scholar
Reddy, C.R., Bhat, Y.S., Nagendrappa, G. & Jai Prakash, B.S. (2009) Brønsted and Lewis acidity of modified montmorillonite clay catalysts determined by FT-IR spectroscopy. Catalysis Today, 141, 157–160.Google Scholar
Sartori, G. & Maggi, R. (2009) Advances in Friedel-Crafts Acylation Reactions: Catalytic and Green Processes. CRC Press, Boca Raton, Florida, USA.Google Scholar
Smith, L.R. (1996) Rheosmin (raspberry ketone) and zingerone and their preparation by crossed Aldol-catalytic hydro-genation sequences. The Chemical Educator, 1, 1–18.Google Scholar
Tateiwa, J.I., Horiuchi, H., Hashimoto, K., Yamauchi, T. & Uemura, S. (1994a) Cation-exchanged montmorillon-ite-catalyzed facile Friedel-Crafts alkylation of hydroxyl and methoxy aromatics with 4-hydroxybu-tan-2-one to produce raspberry ketone and some pharmaceutically active compounds. Journal of Organic Chemistry, 59, 5901–5904.Google Scholar
Tateiwa, J., Nishimura, T., Horiuchi, H. & Uemura, S. (1994b) Rearrangement of alkyl phenyl ethers to alkylphenols in the presence of cation-exchanged montmorillonite (Mn+-mont). Journal of the Chemical Society, Perkin Transactions 1, 23, 3367–3371.Google Scholar
Thomas, J.M. & Thomas, W.J. (1997) Principles and Practice of Heterogeneous Catalysis. Wiley-VCH, Weinheim, Germany.Google Scholar
Varma, R.S. (2002) Clay and clay-supported reagents in organic synthesis. Tetrahedron, 58, 1235—1255.Google Scholar
Venkatesha, N.J., Jai Prakash, B.S. & Bhat, Y.S. (2015) The active site accessibility aspect of montmorillonite for ketone yield in ester rearrangement. Catalysis Science and Technology, 5, 1629–1637.Google Scholar
Venuto, P.B., Hamilton, L.A. & Landis, P.S. (1966) Organic reactions catalyzed by crystalline aluminosilicates: II. Alkylation reactions: Mechanistic and aging considerations. Journal of Catalysis, 5, 484–93.Google Scholar