Gas chromatographic identification of chlorination products of aliphatic ketones

Chlorinated derivatives of aliphatic ketones are a class of organic compounds poorly characterized by both mass spectra and chromatographic retention indices up to present. It is caused by objective difficulties of isolation of individual products from reaction mixtures formed in the result of non-selective chlorination of parent carbonyl compounds. Nevertheless the differences of GC retention indices for structurally analogous chlorination products of different ketones and initial substrates indicate the constancy depending on the number and position of chlorine atoms in the molecules. This feature permits us to use the simplest kind of additive schemes in identification of such chlorinated derivatives, including diastereomeric α,α'-dichloro-k-alkanones (k>2). Hence, the identification of chlorination products of aliphatic ketones becomes possible for any compounds of this class without using mass spectrometric data only in the result of accurate measurement of their GC retention indices.     

Rate Constants of Halogen Abstraction from Halogenating Agents by Alkyl Radicals

A procedure has been developed for determination of the relative rate constants for halogen transfer from a number of halogenating agents to alkyl radicals by the competing reactions technique. In combination with the known data, the developed procedure allows estimation of absolute rate constants of the halogen transfer stage.     

Regularities of Pd/C-catalyzed reduction of trichlorobiphenyls with 2-propanol in basic medium

Reduction of a series of trichlorobiphenyls with 2-propanol in basic medium catalyzed by Pd/C has been studied. Regioselectivity of the reduction has been determined. In the studied cases, the chlorine atom in para or meta positions of the more substituted ring has been more reactive. Using isotope labeling, it has been demonstrated that the reaction occurs via the stage of 2-propanol dehydration on palladium catalyst, followed by catalytic hydrogenation of the polychlorinated biphenyls.