Selectivity in the Photochlorination of 2,3-Dimethylbutane with Molecular Chlorine in Noncomplexing Solvents

Article abstract of DOI:10.1021/jo00257a005

The factors affecting changes in the measured selectivity for the photochlorination of 2,3-dimethylbutane (DMB) in alkane solvents and in CCl4 have been identified.At low chlorine concentrations in CCl4 as solvent, the selectivities, S^m = <2-ClDMB>/<1-ClDMB>, are dramatically enhanced because of CCl4 and Cl3C-radical participation in the overall chain process.In the absence of CCl4, the selectivities may also increase at very low chlorine concentrations because residual O2 and peroxyl radicals participate in the overall chain process.In the absence of either of the above phenomena, S^m was calculated to be 0.64, a value that compares well with a value of 0.62, which we have measured in the gas phase.