Synthesis of benzylidenecycloalkan-1-ones and 1,5-diketones under Claisen–Schmidt reaction: Influence of the temperature and electronic nature of arylaldehydes

ABSTRACT

Herein, we present the results of the influence of reaction temperature and the electronic nature of arylaldehydes in the reactions of benzocycloalkan-1-ones and arylaldehydes under classical Claisen–Schmidt condensation conditions. The products obtained, 2-arylidene derivatives of benzocycloalkan-1-ones and/or spiropolycyclic-1,5-diketones through multicomponent reactions, depended on the electronic nature of arylaldehyde and the reaction temperature. Besides, under identical conditions, 2-arylideneindan-1-ones afforded bis-indane-1,5-diketones through a process that involves Michael addition reaction, which is also dependent on the temperature. Theoretical studies using density-functional theory allowed understanding the chemical reactivity and the site selectivity of α,β-enones used in this work through the calculation of global and local electrophilicity on C–β. Both the electrophilicity of C-β and the temperature led the course of reaction toward the formation of aldol condensation, aldol condensation/Michael addition, and aldol condensation/dimerization products. This work is the first to perform the structural and configurational assignments of bis-indane-1,5-diketones.

GRAPHICAL ABSTRACT

KEYWORDS:

• Aldolic condensation
• benzocycloalkan-1-ones
• bis-indane-1,5-diketones
• Michael addition
• spiropolycyclic-1,5-diketones

Acknowledgment

This study was supported by Universidad Nacional de Luján.