Organska kemija (Slovene)

In our continuing research on the field of chemistry of fluorinated organic molecules we discovered a method for selective synthesis of derivatives of 4-fluorocyclohexa-2,5-dienones from para substituted phenols following the reactions with N-fluoro-diazoniabicyclo[2.2.2]octan bis tetrafluoroborate salts analogues. The method was found to be useful also for the mentioned fluorofunctionalisation of steroids possessing hydroxy or methoxy derivatised aromatic ring A. We used analogue reaction for the transformation of hindered phenols selectively to para quinol derivatives. We had further improved in our laboratory discovered method for selective ?-carbonyl fluorofunctionalisation of ketones using F-TEDA-BF4 or NFTh and by choosing an appropriate solvent (acetonitrile or methanol) in the case of activated aromatic ketones we succeeded to selectively direct the course of the reaction towards aromatic ring or ?-carbonyl fluorofunctionalisation. Kinetic investigations of the reactions of phenyl-substituted alkenes with F-TEDA-BF4 or NFTh enabled us to get valuable informations helping us in mechanistic elucidations of these reactions. We confirmed the second order kinetics and established only small effect of solvent polarity on the rate constants for studied reactions indicating little change in the polarity of the rate determining transition state in comparison with the reactants. We proposed as the most probable reaction mechanism the formation of not markedly polar ?-complex which over the ß-carbonium ion intermediate transfomed to products. Our collaboration with Jean-Piere Begue group from CNRS BIOCIS, Universite Paris-Sud resulted in the Marie Curie fellowship for our member dr. Jernej Iskra, who will next year start the postdoc study in the french partner group. The collaboration with Iskra-Batteries Zmaj inc. resulted in the development of Hg and Pb free alcaline zinc/air batteries.