Timothy R. Demmin

PREPARATION, FLUORINATION AND SYNTHETIC UTILITY OF A CFC-OLEFIN ADDUCT

Abstract 1,1,1 -Trichlorotrifluoroethane was added to ethylene using the catalyst system Fe/triethylphosphite, which eliminated the need for a solvent and avoided the corrosion problems inherent in CuCl-catalyzed reactions. The adduct, CF 3 CCl 2 CH 2 CH 2 Cl, was fluorinated with HF over a chromium(III) oxide catalyst. A series of alternating dehydrochlorinations and HF additions to internal C=C double bonds was proposed and supported by thermodynamic calculations to explain the formation of CF 3 CF 2 CH=CH 2 as the principal fluorination product. An intermediate, CF 3 CCl=CHCH 2 Cl, formed cleanly by dehydrochlorination of the adduct in the absence of HF, was converted into 4,4,4- trifluorobutanol and other compounds of the type CF 3 CCl=CHCH 2 X (X = OAc, OH, Br, I, H).

Copper(II)-Induced Oxygenolysis of o-Benzoquinones, Catechols, and Phenols: The Active Copper(II)-Species, Role of Cupric Chloride, and the General Question of Activation of Molecular Oxygen by Dioxygenases

The chemical energy required by biological systems to do work is derived primarily by oxidation of complex organic molecules to carbon dioxide and water. Since, in the overall process, oxygen acts as a final acceptor of electrons from the substrates and is converted to water, a special mechanism for the activation of molecular oxygen is not required. Nevertheless, it is still not known with certainty whether the required four electrons are transferred between the last few members of the electron-transporting chain in pairs or singly, nor is it known precisely how molecular oxygen accepts the electrons from the last member of this chain (the cytochrome c oxidase). 1