Abstract
A group of nine phenylynamines (PhC⋮CNH2, PhC⋮CNHCH(CH3)2, PhC⋮CNHC6H11, PhC⋮CNHC6H5, PhC⋮CNHC6F5, PhC⋮CN(CH2)5, PhC⋮CN(CH2CH2)2O, PhC⋮CN(CH2CH2CN)2, and PhC⋮CN(CH3)C6F5) were generated in aqueous solution by flash photolyic decarbonylation of the corresponding phenylaminocyclopropenones, and the kinetics of their facile decay in that medium were studied. This decay is catalyzed by acids for all ynaminesprimary, secondary, and tertiaryand also by bases for primary and secondary ynamines. Solvent isotope effects and the form of acid−base catalysis show that the acid-catalyzed path involves formation of keteniminium ions by rate-determining proton transfer to the β-carbon atoms of the ynamines. The ions generated from primary and secondary ynamines then lose nitrogen-bound protons to give ketenimines, and the ketenimines obtained from secondary ynamines are hydrated to phenylacetamides, whereas that from the primary ynamine tautomerizes to phenylacetonitrile. Keteniminium ions formed from tertiary ynamines ...
Published Version
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