organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...

, the Menshutkin reaction converts a

tertiary amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent such ...

into a

quaternary ammonium salt In chemistry, quaternary ammonium cations, also known as quats, are positively charged polyatomic ions of the structure , R being an alkyl group or an aryl group. Unlike the ammonium ion () and the primary, secondary, or tertiary ammonium cation ...

by reaction with an

alkyl halide The haloalkanes (also known as halogenoalkanes or alkyl halides) are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely us ...

. Similar reactions occur when tertiary phosphines are treated with alkyl halides. The reaction is the method of choice for the preparation quaternary ammonium salts. Some phase transfer catalysts (PTC) can be prepared according to the Menshutkin reaction, for instance the synthesis of triethyl benzyl ammonium chloride (TEBA) from

triethylamine Triethylamine is the chemical compound with the formula N(CH2CH3)3, commonly abbreviated Et3N. It is also abbreviated TEA, yet this abbreviation must be used carefully to avoid confusion with triethanolamine or tetraethylammonium, for which TEA ...

and benzyl chloride:

Scope

Reactions are typically conducted in polar solvents such as alcohols. Alkyl iodides are superior

alkylating agents Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting al ...

relative to the bromides, which in turn are superior to chlorides. As is typical for an S_N2 process, benzylic, allylic, and α-carbonylated alkyl halides are excellent reactants. Even though alkyl chlorides are poor alkylating agents (''gem''-dichlorides especially so), amines should not be handled in chlorinated solvents such as dichloromethane and dichloroethane, especially at high temperatures, due to the possibility of a Menshutkin reaction. (Sometimes, kinetically facile reactions like acylations are sometimes conducted in chlorinated solvents nonetheless.) Highly nucleophilic tertiary amines like

DABCO DABCO (1,4-diazabicyclo .2.2ctane), also known as triethylenediamine or TEDA, is a bicyclic organic compound with the formula N2(C2H4)3. This colorless solid is a highly nucleophilic tertiary amine base, which is used as a catalyst and reagen ...

will react with dichloromethane at room temperature overnight and at reflux (39-40 °C) over several hours to give the quaternized product (see the article on

Selectfluor Selectfluor, a trademark of Air Products and Chemicals, is a reagent in chemistry that is used as a fluorine donor. This compound is a derivative of the nucleophillic base DABCO. It is a colourless salt that tolerates air and even water. It has ...

). Due to steric hindrance and unfavorable electronic properties, chloroform reacts very slowly with tertiary amines over a period of several weeks to months. Even pyridines, which are considerably less nucleophilic than typical tertiary amines, react with dichloromethane at room temperature over a period of several days to weeks to give bis(pyridinium)methane salts. In addition to solvent and alkylating agent, other factors strongly influence the reaction. In one particular

macrocycle Macrocycles are often described as molecules and ions containing a ring of twelve or more atoms. Classical examples include the crown ethers, calixarenes, porphyrins, and cyclodextrins. Macrocycles describe a large, mature area of chemistry. ...

system the reaction rate is not only accelerated (150000 fold compared to

quinuclidine Quinuclidine is an organic compound and a bicyclic amine and used as a catalyst and a chemical building block. It is a strong base with p''K''a of the conjugate acid of 11.0.{{cite journal , title=Azatriquinanes: Synthesis, Structure, and Reacti ...

) but the halide order is also changed

History

The reaction is named after its discoverer,

Nikolai Menshutkin Nikolai Aleksandrovich Menshutkin (russian: Николай Александрович Меншуткин; – ) was a Russian chemist who discovered the process of converting a tertiary amine to a quaternary ammonium salt via the reaction with a ...

, who described the procedure in 1890.''Lexikon bedeutender Chemiker'' (VEB Bibliographisches Institut Leipzig, 1989) ( Depending on the source, his name (and the reaction named after him) is spelled as Menšutkin, Menshutkin, or Menschutkin.

References

{{DEFAULTSORT:Menshutkin Reaction Substitution reactions Name reactions