Finkelstein reaction


The Finkelstein reaction named after the German chemist Hans Finkelstein, is an SN2 reaction that involves the exchange of one halogen atom for another. It is an equilibrium reaction, but the reaction can be driven to completion by exploiting the differential solubility of halide salts, or by using a large excess of the halide salt.

Method

The classic Finkelstein reaction entails the conversion of an alkyl chloride or an alkyl bromide to an alkyl iodide by treatment with a solution of sodium iodide in acetone. Sodium iodide is soluble in acetone while sodium chloride and sodium bromide are not. The reaction is driven toward products by mass action due to the precipitation of the poorly soluble NaCl or NaBr. An example involves the conversion of the ethyl ester of 5-bromovaleric acid to the iodide:
Potassium fluoride is used for the conversion of chlorocarbons into fluorocarbons.. Such reactions usually employ polar solvents such as dimethyl formamide, ethylene glycol, and dimethyl sulfoxide.

Use for analysis

Alkyl halides differ greatly in the ease with which they undergo the Finkelstein reaction. The reaction works well for primary halides, and exceptionally well for allyl, benzyl, and α-carbonyl halides. Secondary halides are far less reactive. Vinyl, aryl and tertiary alkyl halides are unreactive; as a result, the reaction of NaI in acetone can be used as a qualitative test to determine which of the aforementioned classes an unknown alkyl halide belongs to, with the exception of alkyl iodides, as they yield the same product upon substitution. Below some relative rates of reaction :
Me-ClBu-Cli-Pr-Clt-BuCH2-ClCH2=CH-CH2-ClPhCH2-ClEtOCCH2-ClMeCCH2-Cl
17910.01460.0000364179160033000

In modern usage the definition of the reaction has been expanded to include the conversion of alcohols to alkyl halides by first converting the alcohol to a sulfonate ester, and then performing the substitution. The example below is from a synthesis of chrysochlamic acid.

Aromatic Finkelstein reaction

The aromatic chlorides and bromides are not easily substituted by iodide, though they may occur when appropriately catalyzed. The so-called "aromatic Finkelstein reaction" is catalyzed by copper iodide in combination with diamine ligands. Nickel bromide and tri-n-butylphosphine have been found to be suitable catalysts as well.