Steven Warren - Studies in Field Ionization Kinetics

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  Publication Details (including relevant citation   information):

  Steven   E. Warren, 1978.

  Doctoral   dissertation


  Field ionization studies of substituted acetophenones and their   related 1,3-dioxolanes undergoing methyl group cleavage are   reported. The sigma-rho plot for the para substituted ketones   revealed two different mechanisms in operation. Electron   withdrawing substituents yielded the same increased cleavage rate   relative to acetophenone itself, while the electron donating   substituents yielded the expected sloped line with cleavage rates   dependent on donation capacities of the substituents. It is   proposed that ionization for the electron donating substituted   acetophenones occurs in the substituent or the ring, while   ionization for the electron withdrawing group substituted   acetophenones is primarily ionized on the carbonyl oxygen.

  The related para substituted 1,3-dioxolanes from acetophenones   suggested only a single ionization mechanism by virtue of a   single-sloped linear sigma-rho plot.

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