Journal of Molecular Catalysis A: Chemical 223 (2004) 177–183 Alkylation and acylation of phenol with methyl acetate K. Shanmugapriya, S. Saravanamurugan, M. Palanichamy, Banumathi Arabindoo, V. Murugesan ∗ Department of Chemistry, Anna University, Chennai-600025, India Received 4 July 2003; received in revised form 14 March 2004; accepted 22 March 2004 Available online 18 September 2004 Abstract The feasibility of effecting both methylation and acylation of phenol with a single reagent, methyl acetate was investigated over MgZSM- 5, MgY and Mg zeolites at 200, 250, 300, 350, 400 ◦ C with a feed ratio 1:2 (phenol:methyl acetate). The major products were anisole, 2,6-dimethylphenol (2,6-DMP), 2,4-dimethylphenol (2,4-DMP), o-cresol and phenyl acetate. Phenol conversion increased with increase in reaction temperature from 200 to 350 ◦ C but decreased at 400 ◦ C over Mg. Selectivity to anisole also exhibited similar trend. High selectivity to 2,6-DMP, o-cresol and phenyl acetate was noted at 350 ◦ C. Selectivity to 2,4-DMP was not as high as 2,6-DMP. Increase in methyl acetate content in the feed increased the conversion, but a decrease in conversion was noted at the feed ratio 1:7. The activity of the catalysts at 400 ◦ C followed the order Mg > MgZSM-5 ≈ MgY which was also the order of Lewis acidity. Increase in WHSV decreased the conversion. The study of time on stream showed decrease in conversion with increase in stream. © 2004 Elsevier B.V. All rights reserved. Keywords: Acylation; Zeolites; Methyl acetate; Phenol; Methylation 1. Introduction Acylation reactions are largely employed in fine chem- ical industry to produce a variety of synthetic fragrances and pharmaceuticals [1,2]. The acylation of aromatics has been generally carried out with Bronsted or Lewis acid cat- alysts [3,4]. Hydroxyacetophenones, which are required in the production of pharmaceuticals, stand out among the aro- matic products. These compounds can be obtained by di- rect C-acylation of phenol with acetic acid or rearrangement of phenyl acetate. Obviously, the first route is more inter- esting since it employs readily available and less expensive raw materials. Due to the greater electron density of pheno- lic oxygen, the formation of hydroxyacetophenones occurs essentially through O-acylation and ester formation. Several authors have studied this route in liquid phase [5] or gas phase [6]. In both cases, the primary product is phenyl acetate and o- hydroxyacetophenone (OHAP) is the secondary product. Ad- ditionally, for kinetic reasons, the phenyl acetate formation is ∗ Corresponding author. Tel.: +91 44 22200660; fax: +91 44 22200660. E-mail address: v murugu@hotmail.com (V. Murugesan). much faster than its isomerisation. Acylation has been done with acetic acid [7,8], acetic anhydride [9] and acetyl chloride [10,11] over acid–base catalysts. Lewis acid catalysts such as AlCl 3, BF 3 and ZnCl 2 are the commonly used catalysts in this reaction [1,2]. But, Lewis acid catalysts have drawbacks because they produce heavy inorganic wastes necessitating disposal problems. Hence the use of solid acid catalysts such as zeolite is advantageous for both acylation and alkylation as they are ecofriendly. The use of acetic acid is also not advantageous for acylation as it would leach out framework aluminium. Similarly acetic anhydride is also not advanta- geous as acetic acid is produced as one of the products. In the present study, the feasibility of effecting simultaneously both methylation and acylation of phenol using methyl ac- etate over Mg 2+ ion-exchanged ZSM-5, Y and  zeolites was investigated and the results are discussed in this paper. 2. Experimental The parent NaY, Na and NaZSM-5 zeolites were pro- vided by Sud chemie India Ltd. These catalysts were sub- 1381-1169/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molcata.2004.03.061