Gas-Phase Reactions of Negative Ions with Alkyl Nitrites

Article abstract of DOI:10.1021/ja00414a016

The gas-phase reactions of F^-, NH2^-, OH^-, and a variety of carbanions with a series of alkyl nitrites (methyl, ethyl, n-butyl, isoamyl, and neopentyl) are reported.The reactions of F^- were studied by the selected ion flow tube technique while all other reactions were examined in a conventional flowing afterglow system.For fluoride ion, E2 reactions occur exclusively for nitrites containing β-hydrogens, S_N2 processes dominate for methyl nitrite, and E_CO2 reactions occur for neopentyl nitrite.The high specificity of product formation is discussed in terms of potential surfaces, and reaction rate constants are compared to calculated collision rates.The reactions of carbanions with neopentyl nitrite proceed primarily by nitrosation followed by proton transfer or by nitrosation followed by a reverse Claisen-type condensation.Finally, NH2^- and OH^- react rapidly with most nitrites to form NO2^-; NH2^- reacts with neopentyl nitrite to generate HN2O^-.These data are compared and contrasted to some recent results from ion cyclotron resonance experiments.