Halogenation of Nonaromatic Compounds

The halogenation of saturated aliphatic hydrocarbons is usually achieved by free radical processes.523 Ionic halogenation of alkanes has been reported under superacid catalysis. Olah and co-workers524,525 have carried out chlorination and chlorolysis of 

Prakash, and co-workers533 have reported the electrophilic fluorination of methane with N2F+ and NF4+ salts serving as F+ equivalents in pyridinium 

Cyclopropane -15, 10 n-Propyl chloride (40.0), Isopropyl chloride (31.5), 1,3-Dichloroporpane (1.2) 

Reaction conditions Cl2 AgSbF6 alkane molar ratio = 5 1 10, CH2C12 as solvent. Analysis by gas chromatography. 

Selective monohalogenation (chlorination and bromination) can be accomplished with excess methylene halides in the presence of SbF5.535 Adamantane, for example, gives 1-chloroadamantane in 80% yield at ambient temperature in 24 h. 

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