Synthèse et réactivité dans le domaine des benzocyclènes tricycliques

Abstract : The work is devoted to the study of the reactivity of bi and tricyclic benzocyclenes haevy one aromatic ring condensed with one or two cycloalkanes with 5,6 or 7 carbons atoms (for example : indane and tetrahydro-2a,3,4,5 acenaphtene). The aim is to show the influence of the ring size on the reactivity of the aromatic system, effect know as Mills Nixon effect. A litterature survey underline the difficulties encountered in demonstrating this effect. A first step was the synthesis of the compounds usually not commercially available. Concerning the reactivity, two approaches have been used : a) study of electrophilic substitutions - Friedel Crafts acetylation and bromination b) kinetics of protodesylilation. In case of bromination, a prealable synthesis of all the bromo derivatives has allowed the characterization of the substitution position. From the bromoderivation, the trimethylsilyl derivatives have been prepared for use in the kinetic study. The results show in a very coherent a desactivation of the beta position in every case, explained by the hyperconjugaison effect in the transition states. Its seems that the deactivation, in alpha position of the cyclopentane ring is at the origine of the Mills Nixon effect. Of low intensity, even lowered by steric hindrance, the desactivation can be explained in satisfying manner using Streitwieser's hybridation model
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René Gruber. Synthèse et réactivité dans le domaine des benzocyclènes tricycliques. Chimie organique. Université Paul Verlaine - Metz, 1986. Français. ⟨NNT : 1986METZ024S⟩. ⟨tel-01775563⟩

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