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*Revision Materials and Past Papers* 1 Atomic Structure 2 Amounts of Substance 3 Bonding 4 Energetics 5 Kinetics 6 Chemical Equilibria & Kc 7 Redox Equations 8 Thermodynamics 9 Rate Equations 10 Kp (Equilibrium Constant) 11 Electrode Potentials & Cells 12 Acids and Bases 13 Periodicity 14 Group 2: Alkaline Earth Metals 15 Group 7: The Halogens 16 Period 3 Elements & Oxides 17 Transition Metals 18 Reactions of Ions in Aqueous Solution 19 Intro to Organic Chemistry 20 Alkanes 21 Halogenoalkanes 22 Alkenes 23 Alcohols 24 Organic Analysis 25 Optical Isomerism 26 Aldehydes & Ketones 27 Carboxylic Acids & Derivatives 28 Aromatic Chemistry 29 Amines 30 Polymers 31 Amino Acids, Proteins & DNA 32 Organic Synthesis 33 NMR Spectroscopy 34 Chromatography RP1–RP12 Required Practicals

3.11 Amines (A-level only)

3.11.1 Preparation (Amines) 3.11.2 Base Properties (Amines) 3.11.3 Nucleophilic Properties (Amines)

Nucleophilic Properties of Amines

Specification Reference Organic chemistry, Amines 3.3.11.3

Quick Notes

  • Amines can act as nucleophiles due to the lone pair of electrons on the nitrogen atom, which can attack electron-deficient species.
    • Nucleophiles are electron pair donors.
  • Amines undergo nucleophilic substitution with halogenoalkanes to form:
    • Primary, secondary, tertiary amines and quaternary ammonium salts.
    AQA A-Level Chemistry schematic showing primary to tertiary amines and quaternary ammonium salt formation via nucleophilic substitution
  • Quaternary ammonium salts are used as cationic surfactants in detergents and fabric softeners.
  • Amines also undergo nucleophilic addition–elimination reactions with acyl chlorides and acid anhydrides to form amides.
  • AQA A-Level Chemistry overview showing amide formation from amines with acyl chlorides or acid anhydrides

Full Notes

Nucleophilic Substitution with Halogenoalkanes

Amines undergo nucleophilic substitution with halogenoalkanes to form primary, secondary, tertiary amines and quaternary ammonium salts.

AQA A-Level Chemistry diagram showing successive substitution steps from primary to tertiary amines and quaternary ammonium salt

The lone pair of electrons on the Nitrogen atom enable them to act as nucleophiles (electron pair donors).

The reactions follow a nucleophilic substitution mechanism:
(see Halogenoalkanes for more detail)

AQA A-Level Chemistry Excess ammonia in ethanol giving a primary amine from a halogenoalkane

Uses of Quaternary Ammonium Salts

Quaternary ammonium salts (R4N+X) are used as cationic surfactants.

Applications:
Fabric softeners
Hair conditioners
Detergents

How They Work:

AQA A-Level Chemistry schematic of cationic surfactant action with hydrophobic tail on grease and positively charged head in water

Nucleophilic Addition–Elimination with Acyl Chlorides and Acid Anhydrides

Amines react with acyl chlorides and acid anhydrides to form amides.

AQA A-Level Chemistry overview showing amide formation from amines with acyl chlorides or acid anhydrides

Mechanism: Nucleophilic addition–elimination.

Reagents: Acyl chloride (RCOCl) + Ammonia/Primary Amine.

ExampleReaction (Primary Amine with acyl chloride — example of ethanoyl chloride + ethylamine):

AQA A-Level Chemistry example reaction of ethanoyl chloride with ethylamine to form an N-substituted amide

Amines react similarly with acid anhydrides, however carboxylic acids are also formed.

AQA A-Level Chemistry reaction of acid anhydride with ammonia to form an amide and a carboxylic acid AQA A-Level Chemistry reaction of acid anhydride with a primary amine to form an N-substituted amide and a carboxylic acid

Summary