Radical Reactions

Radical thermochemistry and organic reactions*

Most free radicals are transient species and it is therefore difficult to measure their thermochemical properties. We have used two new techniques that address this problem. Photoacoustic calorimetry was used to measureheats of formation of free radicals and thus homolytic bond strengths, while photomodulated voltammetry was used to measure their oxidation and reduction potentials. The data off...

Biological radical sulfur insertion reactions.

ion at C-6 results in an allylic radical in which spin delocalization of the radical center makes it reactive with respect to the protein itself and thus results in covalent binding. b. Biotin Synthase is a Member of the RadicalSAM Family. Biotin synthase has been proposed to belong to the radical-SAM enzyme family for the following reasons.75 First it contains a (4Fe-4S)2+/1+ cluster required ...

Radical-radical cross coupling reactions of photo-excited fluorenones.

Radical-radical cross coupling reactions of photoexcited 9-fluorenones have been accomplished for the first time, leading to the synthesis of 9-alkyl, pyrollidinyl and spiro-THF derivatives of 9-fluorenones. The method also reveals, for the first time, the behaviour of ketyl radicals in decarboxyaltive alkylation and ring expansion reactions.

Radiolysis of Liquid Propane: Radical Reactions

The radical reactions in the liquid phase y-radiolysis of propane have been studied from -130 to 35°C and compared with the gas-phase radiolysis at 35°C. Oxygen was used as a scavenger 10 separate thermal radical yields, and effects· of phase and temperature on the radical yields were assessed. The gas-liquid phase change (a) decreases total decomposition by about 14 %, (b) increMCs disproporti...

Organic Peroxides in Radical Synthesis Reactions