Acetylation of 2-methoxynaphthalene (2MN) with acetic anhydride (AA) was ca
rried our over a HBEA 15 zeolite (framework Si/Al ratio of 15) under the fo
llowing conditions: batch reactor, 500 mg of zeolite, 35 mmol of 2MN and 7
mmol of AA, 4 cm(3) of solvent, temperature of 90 degrees C, 120 degrees C
or 170 degrees C (generally 120 degrees C). In addition to acetic acid, the
main reaction products are 1-acetyl-2-methoxynaphthalene (I) and 2-acetyl-
6-methoxynaphtalene (LI); 1-acetyl-7methoxynaphthalene (III) is formed in l
ow amounts and 2-acetyl-3-methoxynaphthalene (IV) in trace amounts. I, whic
h initially is preferentially formed, undergoes isomerization into II and I
II and also deacylation afterwards, However, high yields into isomer II, wh
ich is a precursor of the anti-inflammatory Naproxen, can be obtained by op
erating at relatively high temperatures (greater than or equal to 170 degre
es C) in the presence of a solvent of intermediate polarity such as nitrobe
nzene. The solvent polarity has a significant effect on the reaction rates
and on the selectivity to acetylation, isomerization and deacylation. Very
polar solvents such as sulfolane, which compete with the reactant molecules
for diffusion inside the zeolite micropores and for adsorption on the acid
sites, reduce significantly the reaction rates. Low acetylation and isomer
ization rates and high deacetylation rates are found with non-polar solvent
s, such as 1-methylnaphthalene which cannot solvate the acylium ion interme
diates. Adsorption experiments suggests that all the acetylmethoxynaphthale
ne products are mainly formed inside the zeolite micropores. (C) 2000 Elsev
ier Science B.V. All rights reserved.