Unit 9 Amines and amino acids
Key unit competence: Evaluate the relationship between the molecular structure of amines and amino acids, their physical and chemical properties and their uses.
Key ideas
- Amines are derivatives of ammonia: primary (RNH2), secondary (R2NH), tertiary (R3N) and quaternary ammonium salts (R4N+). Named as alkylamines (ethylamine) or aminoalkanes; phenylamine (C6H5NH2) is aromatic.
- Physical properties: small amines are gases or volatile liquids with fishy smells, soluble in water (hydrogen bonding); boiling points lower than alcohols of similar mass (N–H...N bonds are weaker).
- Amines are bases (lone pair on N): CH3NH2 + H2O ⇌ CH3NH3+ + OH−. Basic strength: secondary ≈ primary > ammonia > phenylamine (alkyl groups donate electrons; in phenylamine the lone pair is delocalised into the ring).
- Preparation: halogenoalkane + excess ammonia (heat, sealed tube); reduction of nitriles or amides (LiAlH4); reduction of nitrobenzene (Sn/conc. HCl) for phenylamine. Reactions: with acids → salts; with acyl chlorides → amides; with halogenoalkanes → higher amines; phenylamine + nitrous acid (below 10 °C) → diazonium salt → azo dyes.
- Amino acids contain NH2 and COOH on the same carbon (H2N-CHR-COOH); glycine (R = H) is the simplest; all others are chiral (optically active, L-form in nature). In water and in the solid they exist as zwitterions (H3N+-CHR-COO−), giving high melting points and water solubility; they are amphoteric; the pH at which they have no net charge is the isoelectric point.
- Two amino acids join by a condensation reaction forming a peptide (amide) bond (–CO–NH–) and water: dipeptide, polypeptide, protein. Proteins are hydrolysed by acid or enzymes back to amino acids (separated by chromatography and detected with ninhydrin). Uses: amines in dyes, drugs and nylon; amino acids as building blocks of proteins, food supplements.
Common misconceptions
- "Phenylamine is a stronger base than ammonia because it is bigger." No: Phenylamine is weaker: its N lone pair is delocalised into the benzene ring.
- "Amino acids exist mainly as neutral molecules in the solid." No: They exist as zwitterions, which is why they have high melting points.
- "Peptide bonds form by addition with no by-product." No: Peptide bonds form by condensation, eliminating water.
Worked examples
Example 1. Explain the relative basic strengths of ethylamine, ammonia and phenylamine.
Solution
Basicity depends on how available the N lone pair is to accept H+.
Ethylamine: the ethyl group donates electrons (+I effect), increasing electron density on N: stronger base than ammonia.
Phenylamine: the lone pair is delocalised into the benzene ring π system: less available, weaker base than ammonia.
Order: phenylamine < ammonia < ethylamine.
Example 2. Describe the formation and hydrolysis of the dipeptide alanylglycine.
Solution
Formation: the –COOH of alanine reacts with the –NH2 of glycine; water is eliminated (condensation): H2NCH(CH3)CONHCH2COOH.
The –CO–NH– link is a peptide (amide) bond.
Hydrolysis: heat with 6 mol/dm3 HCl (or use enzymes such as proteases); water adds across the peptide bond, giving back alanine and glycine.
Practice questions
Classify: CH3NH2, (CH3)2NH, (CH3)3N.
Show answer
Primary, secondary, tertiary.
Common mistake: Classifying by number of carbons.
Write the equation for methylamine with water.
Show answer
CH3NH2 + H2O ⇌ CH3NH3+ + OH−.
Common mistake: Writing CH3NH2 → CH3NH− + H+.
Why are small amines soluble in water?
Show answer
They form hydrogen bonds with water.
Common mistake: Saying they are ionic.
Write the zwitterion of glycine.
Show answer
H3N+CH2COO−.
Common mistake: Writing H2NCH2COOH only.
What is a peptide bond?
Show answer
The amide link –CO–NH– between amino acids.
Common mistake: Saying an ester link.
Give one use of amines.
Show answer
Dyes, drugs, nylon manufacture, surfactants (any one).
Common mistake: Saying fertiliser only.
Write the product of ethylamine with ethanoyl chloride.
Show answer
N-ethylethanamide.
Common mistake: Writing ethyl ethanoate.
Why is alanine optically active?
Show answer
Its α-carbon has four different groups (H, CH3, NH2, COOH).
Common mistake: Saying it contains nitrogen.
How are amino acids from a protein separated and identified?
Show answer
Hydrolyse; paper chromatography; spray ninhydrin; compare Rf values.
Common mistake: Using distillation.
State why amino acids are amphoteric.
Show answer
They have a basic –NH2 group and an acidic –COOH group.
Common mistake: Saying they are neutral.
Matching and drag-and-drop
Matching
Match each item in column A with the correct answer in column B. Write the letter next to each number.
Column A Column B 1. Amines are basic because: a. detect amino acids on chromatograms (purple spots) 2. Amines smell: b. the nitrogen has a lone pair that accepts H+ 3. The isoelectric point of an amino acid is the pH at which it: c. fishy 4. Ninhydrin is used to: d. has no net charge Show answer
1 → b (the nitrogen has a lone pair that accepts H+) · 2 → c (fishy) · 3 → d (has no net charge) · 4 → a (detect amino acids on chromatograms (purple spots))
- Lewis/Brønsted base.
- Rotting fish contains amines.
- Exists mainly as the zwitterion.
- Locating reagent.
Drag and drop
Choose the correct word or phrase from the box for each gap. One word in the box is not needed.
water · H3N+CH2COOH · peptide (amide) bond · ammonia- Joining two amino acids eliminates .
- The bond joining amino acids in proteins is the .
- In acid solution (low pH), glycine exists mainly as .
Show answer
1: water · 2: peptide (amide) bond · 3: H3N+CH2COOH
- Condensation.
- –CO–NH–.
- Step 1. Acid protonates –COO−.
Step 2. Net positive charge.
Matching
Match each item in column A with the correct answer in column B. Write the letter next to each number.
Column A Column B 1. The simplest amino acid is: a. Ethylamine 2. Amino acids have high melting points because: b. they exist as zwitterions with ionic attractions 3. Which is the strongest base? c. secondary amine 4. CH3NHCH3 is a: d. glycine Show answer
1 → d (glycine) · 2 → b (they exist as zwitterions with ionic attractions) · 3 → a (Ethylamine) · 4 → c (secondary amine)
- R = H.
- Strong electrostatic forces.
- Electron-donating ethyl group.
- Two alkyl groups on N.
Drag and drop
Choose the correct word or phrase from the box for each gap. One word in the box is not needed.
ethylammonium chloride · ethanamide · tin and concentrated HCl · phenols or aromatic amines- Phenylamine is prepared by reducing nitrobenzene with .
- Azo dyes are formed by coupling diazonium salts with .
- Ethylamine reacts with hydrochloric acid to form .
Show answer
1: tin and concentrated HCl · 2: phenols or aromatic amines · 3: ethylammonium chloride
- Then add NaOH.
- Coloured –N=N– compounds.
- Salt formation.