The mechanism of chlorination of hydrocarbons by tert-butyl hypochlorite
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The activation volume effects for chlorination of saturated aliphatic compounds by tert-butyl hypochlorite are different from those observed in the earlier work on tert-butoxy radicals. Chains involving Cl-atoms are established in these systems, their role in the chlorination process becoming more and more significant as the pressure rises.
The selectivity of chlorination in competitive chlorination of aliphatic compound and olefin by tert-butyl hypochlorite increases sharply with an increase in the olefin concentration and activity. This is explained, by partial double-bond addition of the alkyl radicals resulting from H-atom detachment by the tert-butoxy radicals.
The usual method of determining relative rate constants for H-atom detachment by tert-butoxy radicals from the relative amount of monochlorinated products cannot be applied to the chlorination of hydrocarbons by tert-butyl hypochlorite, even if one draws on data from systems containing olefins.
Aromatic solvent have no effect on the composition of the products from the chlorination of hydrocarbons by tert-butyl hypochlorite, the situation here being different from that met in chlorination by chlorine.
KeywordsHydrocarbon Chlorine Alkyl Radical Hypochlorite Relative Rate
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