Photolysis of adamantane-2-spiru-3′-diazirine
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Abstract
The spectral characteristics and photochemical transformations of adamantane-2-spiro-3′-diazirine and its 5-hydroxy derivative were studied. The transformations of the photoexcited molecules of adamantane-2-spiro-3′-diazirine in individual solvents and their mixtures and with various sources of UV radiation were studied by gas-liquid chromatography. The main process in saturated hydrocarbons is the formation of diazoadamantane, which is then converted into adamantanone azine. The addition of small amounts of formic or acetic acid leads to the formation of significant amounts of alkyladamantanes, which are the products from transformations of the intermediately formed carbene adamantylidene. Concurrent transformation paths are also observed in cyclohexene. It is suggested that the adamantylidene is preceded by the formation of an exciplex of diazirine with the polar solvent molecule. The ambiphilic nature of adamantylidene in the photolysis of diazirines was demonstrated by concurrent carbenylation.
Keywords
Hydrocarbon Cyclohexene Photolysis Carbene Solvent MoleculePreview
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