Vinyl‐Kationen, I. Umlagerungen von Homopropargyl‐Verbindungen zu kleinen Ringen

Primare Homopropargylsulfonate (7: R = Alkyl, X = OSO2R′) ergeben bei Solvolyse in Losungsmitteln geringer Nucleophilie (Ameisensaure, Trifluoressigsaure) bevorzugt 2-Alkylcyclobutanone (11: R = Alkyl). Der Einflus der Substituenten an der Dreifachbindung auf die Richtung der Umlagerung wird untersucht. Sekundare Homopropargylsulfonate (18: X = OSO2R′) ergeben bei der Solvolyse geringere Ausbeuten an Cyclobutanonen. Die Solvolyse primarer Homopropargylsulfonate in Gegenwart von Quecksilbersalzen fuhrt bevorzugt zu Alkyl-cyclopropyl-ketonen. Vinyl Cations, I. Rearrangements of Homopropargyl Compounds to Small Rings Primary homopropargyl sulfonates (7, R = alkyl, X = OSO2R′) yield on solvolysis in solvents of low nucleophilic character (formic acid, trifluoroacetic acid) predominantly 2-alkyl-cyclobutanones (11, R = alkyl). The influence of substitution at the acetylenic carbon atom on the direction of rearrangement has been investigated. Secondary homopropargyl sulfonates (18, X = OSO2R) yield on solvolysis smaller amounts of cyclobutanones. Solvolysis of primary homopropargyl sulfonates in presence of mercuric salts yields predominantly alkylcyclopropyl ketones.

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