| The kinetics of three different systems of radical reactions were determined, using laser flash photolysis and competition kinetic methods. Organic synthesis was used to develop models for larger, more complex biological molecules.;In the first part of this thesis, the kinetics of 1,5- and 1,6-hydrogen atom transfer reactions in models for polyunsaturated fats (PUFAs) were investigated using laser flash photolysis. The rate constants for these reactions were found to be on the order of other known radical reactions in PUFAs, thus hydrogen atom transfer reactions may compete with them. The kinetics of alpha-hydroxy radical cyclization reactions were studied in the second part of this thesis. Laser flash photolysis was used to determine the rate constants and Arrhenius functions of these reactions, and a previously unreported method of generating alpha-hydroxy radicals is discussed. Finally, in the last part of this thesis, the Grignard formation reaction of 2-chloro-1,1,1-triphenyl ethane serves as the arena for a kinetic study of 1,2 phenyl migration under radical forming conditions. |
