Kinetic and Theoretical Consideration of 3,4- and 3,5-Dimethoxybenzoyl Chlorides Solvolyses

Bulletin of the Korean chemical society

Dennis N. Kevill¹  Kyoung-Ho Park¹ 

关键词: Dimethoxybenzoyl chloride;    Extended Grunwald-Winstein equation;    Resonance effect;    Kinetic solvent isotope effect;    Activation parameters;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The solvolysis rate constants of 3,4- (1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at 25.0 oC, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4- methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two –OCH3 groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

【 授权许可】

Unknown