a reactivity-selectivity study of the friedel-crafts acetylation of 3,3′-dimethylbiphenyl and the oxidation of the acetyl derivativesreactivity-selectivity研究3、傅克酰化的3u2032-dimethylbiphenyl和氧化乙酰衍生品.pdfVIP

Titinchi et al. Chemistry Central Journal 2012, 6:52 /content/6/1/52 SHORT REPORT Open Access A reactivity-selectivity study of the Friedel-Crafts acetylation of 3,3′-dimethylbiphenyl and the oxidation of the acetyl derivatives 1* 2 1 3* Salam JJ Titinchi , Fadhil S Kamounah , Hanna S Abbo and Ole Hammerich Abstract Background: Friedel-Crafts acetylation is an important route to aromatic ketones, in research laboratories and in industry. The acetyl derivatives of 3,3′-dimethylbiphenyl (3,3′-dmbp) have applications in the field of liquid crystals and polymers and may be oxidized to the dicarboxylic acids and derivatives that are of interest in cancer treatment. Findings: The effect of solvent and temperature on the selectivity of monoacetylation of 3,3’-dmbp by the Perrier addition procedure was studied using stoichiometric amounts of reagents. 4-Ac-3,3′-dmbp was formed almost quantitatively in boiling 1,2-dichloroethane and this is almost twice the yield hitherto reported. Using instead a molar ratio of substrate:AcCl:AlCl3 equal to 1:4:4 or 1:6:6 in boiling 1,2-dichloroethane, acetylation afforded 4,4′- and 4,6′-diacetyl-3,3′-dmbp in a total yield close to 100%. The acetyl derivatives were subsequently converted to the carboxylic acids by hypochlorite oxidation. The relative stabilities of the isomeric products and the corresponding σ-complexes were studied by DFT calculations and the data indicated that mono- and diacetylation followed different mechanisms. Conclusions: Friedel-Crafts acetylation of 3,3′-dmbp using the Perrier addition procedure in boiling 1,2- dichloroethane was found to be superior to other recipes. The discrimination against the 6-acetyl derivative during monoacetylation seem