Reactions Nitrile

1 reactions

1.1 hydrolysis
1.2 reduction
1.3 alkylation
1.4 nucleophiles
1.5 miscellaneous methods , compounds

reactions

nitrile groups in organic compounds can undergo variety of reactions depending on reactants or conditions. nitrile group can hydrolyzed, reduced, or ejected molecule cyanide ion.

hydrolysis

the hydrolysis of nitriles rcn proceeds in distinct steps under acid or base treatment achieve carboxamides rc(=o)nh2 , carboxylic acids rcooh. hydrolysis of nitriles carboxylic acids efficient. when conducted base or acids, reactions cogenerate salts, can problematic.

the kinetic studies show second-order rate constant hydroxide-ion catalyzed hydrolysis of acetonitrile acetamide 1.6 × 10, slower hydrolysis of amide carboxylate (7.4 × 10 m s). thus, base hydrolysis route afford amides contaminated carboxylate. acid catalyzed reactions requires careful control of temperature , of ratio of reagents in order avoid formation of polymers, promoted exothermic character of hydrolysis. mechanism depicted in enlisted link.

reduction

nitriles susceptible hydrogenation on diverse metal catalysts. reaction can afford either primary amine (rch2nh2) or tertiary amine ((rch2)3n), depending on conditions. in conventional organic reductions, nitrile reduced treatment lithium aluminium hydride amine. reduction imine followed hydrolysis aldehyde takes place in stephen aldehyde synthesis, uses stannous chloride in acid.

alkylation

alkyl nitriles sufficiently acidic form nitrile anions, alkylate wide variety of electrophiles. key exceptional nucleophilicity small steric demand of cn unit combined inductive stabilization. these features make nitriles ideal creating new carbon-carbon bonds in sterically demanding environments use in syntheses of medicinal chemistry. recent developments have shown nature of metal counter-ion causes different coordination either nitrile nitrogen or adjacent nucleophilic carbon, profound differences in reactivity , stereochemistry.

nucleophiles

the carbon center of nitrile electrophilic, hence susceptible nucleophilic addition reactions:

with organozinc compound in blaise reaction
with alcohols in pinner reaction.
with amines, e.g. reaction of amine sarcosine cyanamide yields creatine
nitriles react in friedel–crafts acylation in houben–hoesch reaction ketones

miscellaneous methods , compounds

in reductive decyanation nitrile group replaced proton. decyanations can accomplished dissolving metal reduction (e.g. hmpa , potassium metal in tert-butanol) or fusion of nitrile in koh. similarly, α-aminonitriles can decyanated other reducing agents such lithium aluminium hydride.
nitriles self-react in presence of base in thorpe reaction in nucleophilic addition
in organometallic chemistry nitriles known add alkynes in carbocyanation:







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