Preparation of Alkyl Halides

Following are two methods commonly used to prepare alkyl halides.

Hydrogen halide addition to an alkene

Halogen halides add across carbon‐carbon double bonds. These additions follow Markovnikov's rule, which states that the positive part of a reagent (a hydrogen atom, for example) adds to the carbon of the double bond that already has more hydrogen atoms attached to it. The negative part adds to the other carbon of the double bond. Such an arrangement leads to the formation of the more stable carbocation over other less‐stable intermediates.




Reaction of alcohols with sulfur and phosphorous halides

Alcohols can be converted to alkyl halides by reaction with thionyl chloride, SOCl 2·, phosphorous trichloride, PCl 3·, phosphorous pentachloride, PCl 5·, or phosphorous tribromide, PBr 3. For example, ethyl chloride or ethyl bromide can be prepared from ethyl alcohol via reactions with sulfur and phosphorous halides.