Reaction of CS2/Cl complexes with alcohols studied by pulse radiolysis

The reactivity and selectivity of carbon disulfide-chlorine atom complex (CS2/Cl) for hydrogen atom abstraction from various alcohols were studied by pulse radiolysis technique in carbon tetrachloride at room temperature. The measured absolute rate constants were in the range from 4.0×106 for methanol to 3.5×107 dm3 mol−1 s−1 for cyclopentanol. The hydrogen abstraction selectivity was calculated based on the analysis of partial reactivities. The tertiary/primary selectivities were determined to be 8.2 for α-position and 6.8 for β-position of alcohols.