The Finkelstein reaction named after the German chemist

Hans Finkelstein Hans Finkelstein (17 May 1885, Leipzig, Germany - December 1938) was a German chemist. He is particularly known for the Finkelstein reaction developed by and named after him. Biography Hans Finkelstein came from a liberal Jewish family and ...

, is an S_N2 reaction (Substitution Nucleophilic Bimolecular reaction) that involves the exchange of one

halogen The halogens () are a group in the periodic table consisting of five or six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and tennessine (Ts). In the modern IUPAC nomenclature, this grou ...

atom for another. It is an

equilibrium reaction In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the s ...

, 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. :R–X + X′⁻ R–X′ + X⁻

Method

The classic Finkelstein reaction entails the conversion of an

alkyl chloride An organochloride, organochlorine compound, chlorocarbon, or chlorinated hydrocarbon is an organic compound containing at least one covalently bonded atom of chlorine. The chloroalkane class (alkanes with one or more hydrogens substituted by chlor ...

or an

alkyl bromide Organobromine compounds, also called organobromides, are organic compounds that contain carbon bonded to bromine. The most pervasive is the naturally produced bromomethane. One prominent application of synthetic organobromine compounds is the ...

to an

alkyl iodide Organoiodine compounds are organic compounds that contain one or more carbon–iodine bonds. They occur widely in organic chemistry, but are relatively rare in nature. The thyroxine hormones are organoiodine compounds that are required for he ...

by treatment with a solution of

sodium iodide Sodium iodide (chemical formula NaI) is an ionic compound formed from the chemical reaction of sodium metal and iodine. Under standard conditions, it is a white, water-soluble solid comprising a 1:1 mix of sodium cations (Na+) and iodide anions (I ...

acetone Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour. Acetone is miscibl ...

. Sodium iodide is soluble in acetone while

sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of 22.99 and 35. ...

and

sodium bromide Sodium bromide is an inorganic compound with the formula Na Br. It is a high-melting white, crystalline solid that resembles sodium chloride. It is a widely used source of the bromide ion and has many applications.Michael J. Dagani, Henry J. Ba ...

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-bromo

valeric acid Valeric acid or pentanoic acid is a straight-chain alkyl carboxylic acid with the chemical formula . Like other low-molecular-weight carboxylic acids, it has an unpleasant odor. It is found in the perennial flowering plant ''Valeriana officin ...

to the iodide: :EtO₂C(CH₂)₄Br + NaI → EtO₂C(CH₂)₄I + NaBr

Potassium fluoride Potassium fluoride is the chemical compound with the formula KF. After hydrogen fluoride, KF is the primary source of the fluoride ion for applications in manufacturing and in chemistry. It is an alkali halide and occurs naturally as the rare ...

is used for the conversion of

chlorocarbon An organochloride, organochlorine compound, chlorocarbon, or chlorinated hydrocarbon is an organic compound containing at least one covalently bonded atom of chlorine. The chloroalkane class (alkanes with one or more hydrogens substituted by chlo ...

s into

fluorocarbon Fluorocarbons are chemical compounds with carbon-fluorine bonds. Compounds that contain many C-F bonds often has distinctive properties, e.g., enhanced stability, volatility, and hydrophobicity. Fluorocarbons and their derivatives are commerci ...

s. Such reactions usually employ polar solvents such as

dimethyl formamide Dimethylformamide is an organic compound with the formula ( CH3)2NC(O)H. Commonly abbreviated as DMF (although this initialism is sometimes used for dimethylfuran, or dimethyl fumarate), this colourless liquid is miscible with water and the major ...

ethylene glycol Ethylene glycol ( IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an o ...

, and

dimethyl sulfoxide Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula ( CH3)2. This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds a ...

Use for analysis

Alkyl halides differ greatly in the ease with which they undergo the Finkelstein reaction. The reaction works well for primary (except for neopentyl) halides, and exceptionally well for

allyl In organic chemistry, an allyl group is a substituent with the structural formula , where R is the rest of the molecule. It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, ...

benzyl In organic chemistry, benzyl is the substituent or molecular fragment possessing the structure . Benzyl features a benzene ring () attached to a methylene group () group. Nomenclature In IUPAC nomenclature, the prefix benzyl refers to a substi ...

, and α-carbonyl halides. Secondary halides are far less reactive.

Vinyl Vinyl may refer to: Chemistry * Polyvinyl chloride (PVC), a particular vinyl polymer * Vinyl cation, a type of carbocation * Vinyl group, a broad class of organic molecules in chemistry * Vinyl polymer, a group of polymers derived from vinyl ...

aryl In organic chemistry, an aryl is any functional group or substituent derived from an aromatic ring, usually an aromatic hydrocarbon, such as phenyl and naphthyl. "Aryl" is used for the sake of abbreviation or generalization, and "Ar" is used ...

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 (NaI in acetone at 60 °C):

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(I) iodide Copper(I) iodide is the inorganic compound with the formula CuI. It is also known as cuprous iodide. It is useful in a variety of applications ranging from organic synthesis to cloud seeding. Copper(I) iodide is white, but samples often appe ...

in combination with diamine ligands. Nickel bromide and tri-''n''-butylphosphine have been found to be suitable catalysts as well.

References

{{Reflist Halogenation reactions Substitution reactions Name reactions

Method

Use for analysis

Aromatic Finkelstein reaction

See also

References