Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-heterocycles

Nitro-reduction by the vinyl halide radical cation CH2 = CH-X+ (X = Cl or Br) converts nitroaromatics into arylnitrenium ions, significant intermediates in carcinogenesis, and the present study reports on the scope and regioselectivity of this versatile reaction. The reaction is general for different kinds of substituted nitroaromatics; para/meta substitutents have little effect on the reaction while ortho substitutents result in low yields of arylnitrenium ions. The phenylnitrenium ion PhNH+ can be generated by chemical ionization (CI) of nitrobenzene using 1,2-dichloroethane as the reagent gas or by atmospheric pressure chemical ionization (APCI) of 1,2-dichloroethane solution doped with nitrobenzene. The chemical reactivities of the arylnitrenium ions include one-step ion/molecule reactions with nucleophiles ethyl vinyl ether and 1,3-dioxolanes, respectively, involving the direct formation of new C-N bonds and synthesis of indole and benzomorpholine derivatives. The indole formation reaction parallels known condensed phase chemistry, while the concise morpholine-forming reaction remains to be sought in solution. The combination of collision-induced dissociation (CID) with novel ion/molecule reactions should provide a selective method for the detection of explosives such as TNT, RDX and HMX in mixtures using mass spectrometry. In addition to the reduction of the nitro group, reduction of methyl phenyl sulfone PhS(O)(2)Me to the thioanisole radical cation PhSMe+ occurs using the same chemical ionization reagent 1,2-dichloroethane. This probably involves an analogous reduction reaction by the reagent ion CH2 = CH-Cl+. (J Am Soc Mass Spectrom 2004, 15, 1675-1688) (C) 2004 American Society for Mass Spectrometry.