3.7.2 Nitriles & Hydroxynitriles

• Nitriles are compounds with a -CN functional group
• They can be prepared from the nucleophilic substitution of halogenoalkanes

Propanenitrile, an example of a nitrile

Reaction with KCN

• The nucleophile in this reaction is the cyanide, CN^- ion
• Ethanolic solution of potassium cyanide (KCN in ethanol) is heated under reflux with the halogenoalkane
• The product is a nitrile
  • If an aqueous solution of potassium cyanide (KCN (aq)) is heated under reflux with the halogenoalkane, an alcohol can be formed instead of the nitrile

Bromoethane reacts with ethanolic potassium cyanide when heated under reflux to form propanenitrile

• Hydroxynitriles are compounds with both a hydroxy (-OH) and cyanide (-CN) functional group
• They can be prepared from the nucleophilic addition of aldehydes and ketones

2-hydroxy-2-methylpropanenitrile

Reaction with HCN

• The nucleophilic addition of hydrogen cyanide to carbonyl compounds is a two-step process
• In step 1, the cyanide ion attacks the carbonyl carbon to form a negatively charged intermediate
• In step 2, the negatively charged oxygen atom in the reactive intermediate quickly reacts with aqueous H⁺ (either from HCN, water or dilute acid) to form a 2-hydroxynitrile

The cyanide ion attacks the carbonyl carbon to form a negatively charged intermediate which quickly reacts with a proton to form a 2-hydroxynitrile compound

• Nitriles are hydrolysed by either dilute acid or dilute alkali followed by acidification to give a carboxylic acid
  • Hydrolysis is the breakdown of a compound using water

Hydrolysis of nitriles

• Nitriles are hydrolysed by either dilute acid or dilute alkali followed by acidification
  • Hydrolysis by dilute acid results in the formation of a carboxylic acid and ammonium salt
  • Hydrolysis by dilute alkali results in the formation of a sodium carboxylate salt and ammonia; Acidification is required to change the carboxylate ion into a carboxylic acid

• The -CN group at the end of the hydrocarbon chain is converted to a -COOH group

Hydrolysis of nitriles by either dilute acid (1) or dilute alkali and acidification (2) will form a carboxylic acid