- Photoinduced Nitrene, Carbene, and Atomic Oxygen Transfer Reactions Starting from the Corresponding Pyridinium N-, C-, and O-Ylides
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Ultraviolet irradiation of the pyridinium ylides 1, 2, and 3 led to fragmentation of the exocyclic polar bonds, as well as to skeletal rearrangements.The photoinduced fragmentation processes gave the corresponding pyridines and highly reactive intermediates, i. e. ethoxycarbonylnitrene, dicyanocarbene and atomic oxygen (oxene), respectively.Trapping of the reactive intermediates by alkanes and alkenes permitted the determination of their spin multiplicity.Ethoxycarbonylnitrene was in its triplet ground state at the moment of its formation.Dicyanocarbene occurred as a mixture of singlet and triplet, as determined by dilution experiments with variable amounts of alkenes.As to atomic oxygen, all collected data point to its formation in solution in its triplet ground state.
- Strub, Henri,Strehler, Christiane,Streith, Jacques
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p. 355 - 364
(2007/10/02)
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- Selective imidoylnitrenes
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Two new imidoylnitrenes and alkoxycarbonylnitrene form a sequence of reactivities : Only ROCON attacks CH bonds, it and ROC(NCN)N convert benzene to azepines. Benzene is not attacked by ROC(NSO2CH3)N, but all three nitrenes react with olefins, alcohols, etc.
- Lwowski, Walter,Rao, O.Subba
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p. 727 - 730
(2007/10/02)
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