The acetylation of toluene and benzene with acetyl chloride and bromide and acetic anhydride catalyzed by calcined iron sulfate activated by exposure to a mixture of benzyl chloride and the aromatics.
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The acetylations of toluene and benzene with acetyl halides and acetic anhydride were studied over catalysts prepared by heat-treating FeSO<SUB>4</SUB> in air, followed by activation on exposure to benzyl chloride in toluene or benzene at 40–80 °C for 1 h, together with FeCl<SUB>3</SUB> and AlCl<SUB>3</SUB>. The sulfates treated at 700 and 800 °C showed high activity. The former, activated at 60 °C, gave 68% methylacetophenones, and the latter, more than 90%, with an isomer distribution of 2% <I>ortho</I>-, 1% <I>meta</I>-, and 97% <I>para</I>-form in the reaction of toluene with acetyl halides at room temperature, while the maximum yield was 24% with FeCl<SUB>3</SUB> and 29% with AlCl<SUB>3</SUB>. A high yield of acetophenone, 77%, was obtained over the FeSO<SUB>4</SUB> (700 °C) catalyst in the reaction of benzene with acetyl bromide at 60 °C for 1 h. The present catalysts were also highly active for the acetylation of toluene with acetic anhydride; <I>e.g.</I>, 55% methylacetophenones were obtained over the FeSO<SUB>4</SUB> (800 °C) catalyst at 100 °C for 5 h. FeCl<SUB>3</SUB> and AlCl<SUB>3</SUB> gave quite low yield compared with the present catalysts.
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