I meccanismi delle reazioni che coinvolgono l'anione nitrile dipendono principalmente dalla natura dell'[[elettrofilo]] coinvolto. Le alchilazioni semplici avvengono per spostamento [[Reazione S<sub>N</sub>2SN2| |S<sub>N</sub>2]] (una sostituzione nucleofila bimolecolare)<ref>{{Cita pubblicazione |rivista = [[Organic Reactions|Org. React.]] |autore = A. C. Cope; H. L. Holmes; H. O. House |titolo = The Alkylation of Esters and Nitriles |anno = 1957 |volume = 9 |numero = |pp = 107 |lingua = en |doi = 10.1002/0471264180.or009.04 |isbn= 0471264180 }}</ref> and are subject to the usual stereoelectronic requirements of the process. [[Phase-transfer catalysis]] has been employed in alkylations of arylacetonitriles.<ref>{{cite journal|title=Heterogeneous ethylation of phenylacetonitrile|first1=R. |last1=Solaro |first2=S. |last2=D'Antone |first3=E. |last3=Chiellini |journal=J. Org. Chem. |volume=45 |issue=21 |page=4179 |date=1980|doi=10.1021/jo01309a023}}</ref><ref>{{cite journal|last1=Makosza|first1=M.|last2=Jonczyk|first2=A.|title=Phase-Transfer Alkylation of Nitriles: 2-Phenylbutyronitrile|journal=Organic Syntheses|date=1976|volume=55|page=91|doi=10.15227/orgsyn.055.0091}}</ref> Nitrile anions can also be involved in [[Michael reaction|Michael]]-type additions to activated double bonds and vinylation reactions with a limited number of polarized, unhindered acetylene derivatives.<ref>{{cite journal|title=Reactions of organic anions. XII. Vinylation of phenylacetonitrile derivatives|first=M. |last=Makosza |journal=Tetrahedron Lett. |date=1966|volume=1966|issue=45 |page=5489|doi=10.1016/S0040-4039(00)70128-6}}</ref>
[[File:NitrilePTC.png|center|400px]]
Arylation of nitrile anions is also possible, and can take place through different mechanisms depending on the substrates and reaction conditions. Aryl halides lacking electron-withdrawing groups react through an addition-elimination mechanism involving [[benzyne]] intermediates. Aryl phosphates and ammoniums react through the [[Radical-nucleophilic aromatic substitution|S<sub>RN</sub>1]] pathway, which involves the generation of an aryl radical anion, fragmentation, and bond formation with a nucleophile. Electron transfer to a second molecule of arene carries on the radical chain.
