STUDIES IN THE HALOGENATION OF ALIPHATIC COMPOUNDS
SHEFFIELD UNIV (UNITED KINGDOM)
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The relative rates of the gas phase chlorination of n-hexane at the primary and secondary positions were studied and a rate expression obtained. The chlorination and bromination of 1,1,1-trifluoropentane and 1-fluorobutane were studied in the gas phase using a static system. The reactions were studied at several temperatures and approximate values of the Arrhenius parameters for attack at each site in the molecules were obtained. The results confirm earlier work and show that the CF3 group exerts a very powerful deactivating effect on halogenation at adjacent sites. The chlorination and bromination of n-valeryl fluoride chloride and methyl valerate were studied in the gas phase using a static system. The acyl group deactivates halogenation at adjacent methylene groups, but to a lesser extent at the alpha-position than would be expected on purely polar grounds. The gas phase reaction of fluorine and carbon tetrachloride with nitrogen as a diluent was studied in a flow system. The extent of reaction was followed by determining the halide formed when unchanged fluorine and any fluorine monochloride produced was converted into hydrogen fluoride and hydrogen chloride.
- Inorganic Chemistry