Abstract
Pentanoyl, hexanoyl, and heptanoyl fluorides have been chlorinated at two different temperatures in the gas phase. The corresponding chlorides have also been chlorinated in acetonitrile. The results confirm that in the gas phase a substituent in an aliphatic hydrocarbon chain has no effect on chlorination beyond the β-position. In the solution phase the substituent has a far longer-range effect which seems to be manifest as least to the ε-position for chlorination in acetonitrile. The effect of changes in solvent (from acetonitrile to carbon tetrachloride) has been investigated for esters in addition to acid chloride and found to be comparatively slight.

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