Dimethylaniline

DMA was first reported in 1850 by the German chemist A. W. Hofmann, who prepared it by heating aniline and iodomethane:

C₆H₅NH₂ + 2 CH₃I → C₆H₅N(CH₃)₂ + 2 HI

DMA is produced industrially by alkylation of aniline with methanol in the presence of an acid catalyst:

C₆H₅NH₂ + 2 CH₃OH → C₆H₅N(CH₃)₂ + 2 H₂O

Similarly, it is also prepared using dimethyl ether as the methylating agent.

Dimethylaniline undergoes many of the reactions expected for an aniline, being weakly basic and reactive toward electrophiles.

It is nitrated to produce tetryl, a derivative with four nitro groups which was once used as explosive. In acidic solution, the initial nitration gives 3-nitrodimethylaniline. It reacts with butyllithium to give the 2-lithio derivative. Electrophilic methylating agents like dimethyl sulfate attack the amine to give the quaternary ammonium salt:

C₆H₅N(CH₃)₂ +(CH₃O)₂SO₂ → C₆H₅N(CH₃)₃CH₃OSO₃

Diethylaniline and dimethylaniline are both used as acid-absorbing bases.

DMA is a key precursor to commercially important triarylmethane dyes such as malachite green and crystal violet. DMA serves as a promoter in the curing of polyester and vinyl ester resins. DMA is also used as a precursor to other organic compounds. A study of the in vitro metabolism of N,N-dimethylaniline using guinea pig and rabbit preparations and GLC techniques has confirmed N-demethylation and N-oxidation as metabolic pathways, and has also established ring hydroxylation as a metabolic route.