Aerosol Direct Fluorination: Alkyl Halides II, Chlorine Shifts and the Stability of Radicals.
TENNESSEE UNIV KNOXVILLE DEPT OF CHEMISTRY
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Unlike alkyl bormides and iodides, alkyl chlorides are shown to be stable to direct fluorination, even under ultraviolet irradiation, at temperatures of 30 C and below. Although less reactive than the bromides and iodides, F-alkyl chlorides may be derivatized presenting another example of direct fluorination-survivable functionality. High 63 to moderate 32 isolated yields of the analogous perfluoroalkyl chlorides can be synthesized by aerosol direct fluorination of 1-chloropropane, 1-chlorobutane, 1-chloro-2-methylpropane, 1-chloro-3-methylbutane, 1-chloro-2-methylbutane and chloro-cyclopentane with generally less than 20 precent C-C1 bond cleavage. Tertiary alkyl chlorides generally undergo intramolecular 1,2-chloride shifts in the earliest stages of reaction in a manner characteristic of beta chloro radicals forming principally primary F-alkyl chlorides. Secondary alkyl chlorides undergo a similar but incomplete rearrangement producing mixtures of primary and secondary F-alkyl chlorides.
- Inorganic Chemistry
- Organic Chemistry