A reactivity-selectivity study of the Friedel-Crafts acetylation of 3,3′-dimethylbiphenyl and the oxidation of the acetyl derivatives

Chemistry Central Journal

Ole Hammerich³  Hanna S Abbo¹  Fadhil S Kamounah²  Salam JJ Titinchi¹ 

[1]Department of Chemistry, University of the Western Cape, Private Bag X17, Bellville, 7535, South Africa

[2]CISMI, Department of Science, Systems and Models, Roskilde University, Universitetsvej 1, P.O. Box 260, Roskilde, DK-4000, Denmark

[3]Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, DK-2100, Denmark

关键词: DFT calculations;    Carboxylic acids;    Diacetylation;    Monoacetylation;    3,3′-dimethylbiphenyl;    Friedel-Crafts reaction;   

Others  :  788135
DOI  :  10.1186/1752-153X-6-52

 received in 2012-02-25, accepted in 2012-05-08,  发布年份 2012

【 摘 要 】

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 seems to reflect a mechanism including an AcCl:AlCl₃ complex or larger agglomerates as the electrophile, whereas the less selective diacetylations of the deactivated 4-Ac-3,3′-dmbp are suggested to include the acetyl cation as the electrophile. The DFT data also showed that complexation of intermediates and products with AlCl₃ does not seem to be important in determining the mechanism.

【 授权许可】

   
2012 Titinchi et al.; licensee Chemistry Central Ltd.

【 图 表 】

Scheme 1

Scheme 2

Scheme 3

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