Whiteboard Chemistry with Joe White

Amines

Naming amines the IUPAC way (and the variants AQA accepts), why some amines are stronger bases than others, how they are prepared, and their reactions as nucleophiles — up to quaternary ammonium salts.

AQA 7404/7405 Paper 2 A-level only
Hero motif · to come From ammonia to quaternary
The big idea

An amine is ammonia with one or more hydrogens swapped for carbon groups. That nitrogen still carries a lone pair, and everything on this page flows from it: the lone pair accepts a proton (so amines are bases) and attacks electron-poor carbon (so amines are nucleophiles). We start with the part students most often get wrong — the naming.

Classes & nomenclature

Amines are classified by how many carbon groups are on the nitrogen:

  • Primary (1°) — one carbon group: R–NH2
  • Secondary (2°) — two: R2NH
  • Tertiary (3°) — three: R3N
  • Quaternary ammonium ion — four, giving a permanent positive charge: R4N+

The IUPAC rule

Name amines the same way throughout: take the longest carbon chain attached to the nitrogen as the parent, and add the ending –amine with a locant. Any other group on the nitrogen is written as an N-substituent at the front. So CH3CH2NH2 is ethanamine, and CH3CH2NHCH3 — ethyl chain as parent, methyl on the N — is N-methylethanamine.

IUPAC name vs the variants AQA accepts

Learn one consistent system — the IUPAC –amine names — but recognise the older “–ylamine” style, because AQA mark schemes accept both.

Naming amines — IUPAC (use this) and accepted alternatives
StructureClassIUPAC nameAlso accepted
CH3NH2methanaminemethylamine
CH3CH2NH2ethanamineethylamine
(CH3)2CHNH2propan-2-amine1-methylethylamine / isopropylamine
CH3CH2NHCH3N-methylethanamineN-methylethylamine / methylethylamine
(CH3CH2)2NHN-ethylethanaminediethylamine
(CH3CH2)3NN,N-diethylethanaminetriethylamine
C6H5NH21° aromaticphenylamineaniline (older trivial name)
Figure F1 · illustration to come Four classes, one naming rule Parent = longest chain on N; everything else is an N-substituent.
A quaternary ammonium ion has four carbon groups on N and a permanent positive charge.
🧪 Exam-style questions
Q1 [2 marks]

Bromoethane reacts with methylamine (CH3NH2) to form a secondary amine, CH3CH2NHCH3. Give the IUPAC name of this secondary amine, and state its class.

Show answer

N-methylethanamine (AQA also accepts N-methylethylamine / methylethylamine). 1 mark

It is a secondary (2°) amine — two carbon groups on the nitrogen. 1 mark

Source: AQA A-Level Chemistry past papers.

Why some amines are stronger bases

Amines are weak bases: the nitrogen lone pair accepts a proton (H+). The more available that lone pair, the stronger the base. This single idea explains the whole order:

Reasoning it through the lone pair
  • Aliphatic amine > ammonia: the alkyl groups are electron-releasing (a positive inductive effect). They push electron density onto the nitrogen, so its lone pair is more available to accept a proton — a stronger base than ammonia.
  • Aromatic amine < ammonia: in phenylamine the nitrogen lone pair is delocalised into the benzene ring. It is drawn into the π system and so is less available to accept a proton — a weaker base than ammonia.
Figure F2 · illustration to come How available is the lone pair? Alkyl pushes electrons on; the ring pulls them away.
Everything comes back to whether the N lone pair is more or less available.
🧪 Exam-style questions
Q2 [1 mark]

Which compound is the strongest base?

  1. CH3CH2NH2
  2. C6H5NH2
  3. NH3
  4. CH3CONH2
Ethylamine: the alkyl group pushes electron density onto N, making the lone pair most available. Phenylamine (lone pair delocalised) and the amide (lone pair delocalised onto C=O) are weaker; ammonia sits in between.
Q3 [2 marks]

Explain why 3-aminopentane (CH3CH2CH(NH2)CH2CH3) is a stronger base than ammonia.

Show answer

In 3-aminopentane the lone pair on nitrogen is more available (it accepts a proton more readily). 1 mark

This is because the alkyl groups are electron-releasing / have a positive inductive effect, pushing electron density onto the nitrogen. 1 mark

Source: AQA A-Level Chemistry past papers.

Preparation & reactions

Making amines

There are three routes you need, chosen by what you are starting from:

  • Primary aliphatic amine from a halogenoalkane: heat with an excess of ammonia in ethanol (nucleophilic substitution). The excess ammonia helps stop the amine reacting further.
  • Primary amine from a nitrile: reduce with H2 and a nickel catalyst (or LiAlH4). This adds a carbon to the chain.
  • Aromatic amine from a nitro compound: reduce nitrobenzene with tin and concentrated hydrochloric acid (then add NaOH to free the amine) → phenylamine, used to make dyes.

Amines as nucleophiles

The nitrogen lone pair attacks the δ+ carbon of a halogenoalkane, displacing the halide (nucleophilic substitution). A second ammonia (or amine) then removes H+ to give the free amine. But that product still has a lone pair, so it can react again — the reaction climbs a ladder:

Control the product by choosing what is in excess: excess ammonia favours the primary amine; excess halogenoalkane drives it all the way to the quaternary ammonium salt.

Figures F3 & F4 · illustration to come The mechanism & the ladder to quaternary Excess NH3 → primary; excess halogenoalkane → quaternary.
Each amine formed still has a lone pair, so it can be substituted again.
Quaternary ammonium salts as cationic surfactants

A quaternary ammonium salt has a permanent positive charge on nitrogen and a long hydrocarbon tail. The cationic head binds to negatively charged surfaces (hair, fabric), so these salts are used as cationic surfactants — fabric softeners and hair conditioners.

With acyl chlorides and anhydrides

Ammonia and primary amines also react with acyl chlorides and acid anhydrides by nucleophilic addition–elimination, giving amides and N-substituted amides. That mechanism is drawn in full on the carboxylic acids & derivatives page.

🧪 Exam-style questions
Q4 [1 mark]

Methylamine reacts with bromoethane by nucleophilic substitution to produce a mixture of products. Which is not a possible product of this reaction?

  1. C2H5NHCH3
  2. (C2H5)2NCH3
  3. [(C2H5)3NCH3]+ Br
  4. [(C2H5)2N(CH3)2]+ Br
Methylamine supplies only one methyl group to the nitrogen; bromoethane adds ethyl groups. A product with two methyl groups on N cannot form, so [(C2H5)2N(CH3)2]+ is impossible.
Q5 [2 marks]

Give an equation for the preparation of 1,6-diaminohexane by the reaction of 1,6-dibromohexane with an excess of ammonia.

Show answer

Br(CH2)6Br + 4NH3 → H2N(CH2)6NH2 + 2NH4Br 2 marks

(One mark for both organic structures correct; one for balancing. Each C–Br needs one NH3 to substitute and one to remove the HBr.)

Q6 [3 marks]

1,6-Diaminohexane can also be made in two stages from 1,4-dibromobutane. Suggest the reagent and a condition for each stage.

Show answer

Stage 1 (make the dinitrile): KCN or NaCN, in aqueous ethanol. 1 mark reagent 1 mark condition

Stage 2 (reduce the nitrile groups): H2 with a Ni (or Pt/Pd) catalyst. 1 mark

(The nitrile route adds two carbons, converting a 4-carbon dibromide into the 6-carbon diamine.)

Source: AQA A-Level Chemistry past papers.

Choosing the route

Synthesis questions usually hinge on picking the right preparation. Match the starting material to the method: a halogenoalkane → react with excess ammonia (same carbon count); a shorter chain that needs one more carbon → go via the nitrile (KCN, then reduce); an aromatic nitro compound → reduce with Sn/HCl to the aromatic amine.

The marks that get dropped
  • Base-strength answers that stop at “more electrons” — you must say the lone pair is more (or less) available, and why (alkyl inductive effect; or delocalisation into the ring).
  • Forgetting that the halogenoalkane route gives a mixture — excess ammonia is needed to favour the primary amine.
  • Using NaBH4 to reduce a nitrile — it does not work; use H2/Ni or LiAlH4.
  • A quaternary product needing more of one group than the starting materials can supply (like two methyls from one methylamine).

Examiner reports note that base-strength marks are lost to vague answers: name the effect (positive inductive effect, or delocalisation into the ring) and link it explicitly to the availability of the nitrogen lone pair.

Interactive substitution-ladder explorer loads here. The ladder described above is the static fallback.

🎯 Build the mark scheme — base strength

Explain why ethylamine is a stronger base than ammonia, and why phenylamine is a weaker base than ammonia. Award yourself a mark for each:

  • Ethylamine: the lone pair on N is more available
  • …because the alkyl group is electron-releasing (positive inductive effect).
  • Phenylamine: the lone pair on N is delocalised into the benzene ring
  • …so it is less available to accept a proton.
3.3.11 Amines — Quick-reference summary
  • Classes: 1° (RNH2), 2° (R2NH), 3° (R3N), quaternary ammonium (R4N+).
  • Naming: parent = longest chain on N + –amine; other groups are N-substituents (e.g. N-ethylethanamine). AQA also accepts the –ylamine forms (diethylamine).
  • Base strength: primary aliphatic amine > ammonia > primary aromatic amine. Alkyl groups push electrons onto N (lone pair more available); in phenylamine the lone pair delocalises into the ring (less available).
  • Preparation: 1° aliphatic from NH3 + halogenoalkane (excess NH3) or by reducing a nitrile (H2/Ni); aromatic by reducing a nitro compound (Sn + conc HCl, then NaOH).
  • As nucleophiles: substitution with halogenoalkanes climbs 1°→2°→3°→quaternary; quaternary ammonium salts are cationic surfactants. With acyl chlorides/anhydrides they give amides by addition–elimination.

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Amines reward two habits: naming consistently, and reasoning about the nitrogen lone pair — whether it is more or less available to explain base strength, and where it attacks in a mechanism. Sessions drill both on real AQA past questions.

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