Vinylkationen, 36. Solvolyse von Cycloalkylidenmethyl‐ und 1‐Cyclopenten‐1‐yl‐triflaten

Cyclohexylidenmethyl-triflat (2), Cyclobutylidenmethyl-triflat (5), 1-Cyclopenten-1-yl-triflat (7), Bicyclo[3.1.0]hex-2-en-2-yl-triflat (9), 1-Cyclobutylidenethyl-triflat (19) und 2-Methyl-1-cyclopenten-1-yl-triflat (29) wurden in Losungsmitteln verschiedener Ionisierungsstarke und Nucleophilie solvolysiert und die Solvolyseprodukte aufgeklart. Die Cyclobutylidenalkyl-triflate solvolysieren uber Ionenpaarmechanismen (Vinylkationen) unter Umlagerung zu Cyclopenten- und Cyclopentanon-Derivaten. Die 1-Cyclopenten-1-yl-triflate reagieren nicht uber Vinylkationen als Zwischenstufe, sondern unter OS-Spaltung zu den entsprechenden Ketonen. Vinyl Cations, 36. Solvolysis of Cycloalkylidenemethyl and 1-Cyclopenten-1-yl Triflates Cyclohexlidenemethyl triflate (2), cyclobutylidenemethyl triflate (5), 1-cyclopenten-1-yl triflate (7), bicyclo [3.1.0]hex-2-en-2-yl triflate (9), 1-cyclobutylideneethyl triflate (19), and 2-methyl-1-cyclopenten-1-yl triflate (29) were solvolyzed in solvents of various ionizing power and nucleophilicity and the solvolysis products were identified. The cyclobutylidenealkyl triflates solvolyze via a vinyl cation mechanism involving ion pairs with rearrangement to cyclopentene and cyclopentanone compounds. The 1-cyclopenten-1-yl triflates do not produce vinyl cation intermediates but give only the corresponding ketones via an OS bond cleavage of the triflate group.

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