230. The synthesis and reactions of branched-chain hydrocarbons. Part XV. Free-radical chlorination in the liquid phase

Abstract

Alkanes and cycloalkanes can be chlorinated in the liquid phase by reaction with N , 2,4,6-tetrachloroacetanilide in presence of a small amount of benzoyl peroxide. In this way the relative rates of chlorination of a number of alkanes have been determined by a comparative method. The results support the view that the structure of the hydrocarbon has a marked influence on the rate of chlorination.

Radical reactions of highly polar molecules. Hydrocarbons as chain-transfer agents in fluoro olefin telomerizations

“…The trend of change in the linear alkanes is the same as that observed for photochlorination21 and for benzoyl peroxide catalyzed chlorination with 2,4,6-trichloro-N-chloroacetanilide. 22 The reactivity of the cycloalkanes is less than that expected on the basis of the chlorination results with 2,4,6-trichloro-iV-chloroacetanilide but about the same as expected from the reactivity with methyl radicals23,24 and from chlorination with trichloromethanesulfenyl chloride. 25 The comparison of these results is given in Table II.…”

Liquid Phase Bromination of Decane, Undecane, and Dodecane with N-Bromosuccinimide

“…A product, bp 65 °C (18 mmHg), was shown to be cyclohexyl bromide (46% calculated on the bromoimide). Boocock and Hickinbottom (1963) extended the work to cover bromination of certain normal paraffins. For instance, heptane was refluxed for 14 h with NBS in the presence of benzoyl peroxide to yield 12% of mixed bromoheptanes (bp 59-61 °C (18 mmHg).…”