9701 AS Chemistry — Organic Reactions Reference

Reagents · Conditions · Reaction Types  |  CIE A-Level

📋 Complete Reaction Reference

Reaction types:   Nucleophilic Sub. Electrophilic Add. Elimination Oxidation Reduction Combustion / FRS Hydrolysis Condensation Polymerisation
Substrate Reaction Reagent(s) Conditions Product(s) Type
Alkanes
Alkane Combustion (complete) O₂ (excess) Excess oxygen, ignition CO₂ + H₂O Combustion
Alkane Combustion (incomplete) O₂ (limited) Limited oxygen CO + C (soot) + H₂O Combustion
Alkane Free radical substitution Halogen (Cl₂ or Br₂) UV light Halogenoalkane + HX Free Radical Sub.
Alkenes
Alkene Addition of HBr / HCl HBr(g) or HCl(g) Room temperature, gas or conc. acid Halogenoalkane Electrophilic Add.
Alkene Bromination Br₂ Br₂(l) or Br₂(aq), room temp Dibromoalkane Electrophilic Add.
Alkene Hydration (→ alcohol) Steam (H₂O(g)), H₃PO₄ Heat, conc. H₃PO₄ catalyst Alcohol Electrophilic Add.
Alkene Hydrogenation (→ alkane) H₂(g), Ni catalyst ~150 °C, Ni(s) catalyst Alkane Addition / Hydrogenation
Alkene Oxidation → diol Dilute KMnO₄ Cold, acidic Diol Oxidation
Alkene Oxidation → cleavage Conc. KMnO₄ Hot, acidic Two carbonyl compounds Oxidation
Alkene Polymerisation High pressure, catalyst Poly(alkene) Addition Polymerisation
Halogenoalkanes
Halogenoalkane Substitution → alcohol NaOH (for OH⁻) Heat under reflux, aqueous Alcohol + halide ion Nucleophilic Sub.
Halogenoalkane Substitution → nitrile KCN or NaCN Heat under reflux, ethanolic Nitrile + halide ion Nucleophilic Sub.
Halogenoalkane Substitution → amine Excess NH₃ Heat, ethanolic, sealed tube Amine + ammonium halide Nucleophilic Sub.
Halogenoalkane Elimination → alkene KOH (for OH⁻) Heat under reflux, ethanolic Alkene + KX + H₂O Elimination
Alcohols
Primary alcohol Oxidation → aldehyde K₂Cr₂O₇ / H₂SO₄ (acidified dichromate) Heat gently, distil immediately Aldehyde Oxidation
Primary alcohol Oxidation → carboxylic acid K₂Cr₂O₇ / H₂SO₄ (excess) Heat under reflux Carboxylic acid Oxidation
Secondary alcohol Oxidation → ketone K₂Cr₂O₇ / H₂SO₄ Heat Ketone (no further oxidation) Oxidation
Alcohol Elimination → alkene Conc. H₂SO₄ or H₃PO₄ Heat, acid catalyst Alkene + H₂O Elimination / Dehydration
Alcohol Halogenation (PCl₅) PCl₅(s) Pure / dry alcohol (no water) Chloroalkane + HCl(g) + POCl₃ Halogenation
Alcohol Halogenation (KBr) KBr + conc. H₂SO₄ Warm, distil product Bromoalkane + H₂O Halogenation
Alcohol React with sodium Na(s) Room temperature Alkoxide (RO⁻Na⁺) + H₂ Acid–metal reaction
Alcohol + carboxylic acid Esterification Conc. H₂SO₄ (catalyst) Heat under reflux Ester + H₂O Condensation
Aldehydes & Ketones
Aldehyde Reduction → primary alcohol NaBH₄ Aqueous, room temperature Primary alcohol Reduction
Ketone Reduction → secondary alcohol NaBH₄ Aqueous, room temperature Secondary alcohol Reduction
Carbonyl (aldehyde or ketone) Nucleophilic addition → hydroxynitrile KCN (in dilute acid, H₂SO₄) Aqueous / acidic Hydroxynitrile Nucleophilic Add.
Carboxylic Acids
Carboxylic acid Acid–base (with metal) Metal (e.g. Zn, Mg) Room temperature Metal carboxylate + H₂ Acid–base
Carboxylic acid Acid–base (with alkali) NaOH Room temperature Sodium carboxylate + H₂O Acid–base / Neutralisation
Carboxylic acid Acid–base (with carbonate) CaCO₃ or Na₂CO₃ Room temperature Carboxylate salt + H₂O + CO₂ Acid–base
Carboxylic acid Reduction → primary alcohol LiAlH₄ Dry ether, room temperature Primary alcohol Reduction
Esters & Nitriles
Ester Hydrolysis (acid) Dilute H⁺ (e.g. HCl or H₂SO₄) Warm, aqueous Carboxylic acid + alcohol Hydrolysis
Ester Hydrolysis (alkaline) NaOH(aq) Warm, aqueous Carboxylate salt + alcohol Hydrolysis
Nitrile Acid hydrolysis → carboxylic acid Dilute HCl Heat under reflux Carboxylic acid + NH₄Cl Hydrolysis
Nitrile Reduction → amine LiAlH₄ Dry ether Primary amine Reduction

⚠ Confusable Pairs — The Conditions That Change Everything

1 · Halogenoalkane + OH⁻ → Alcohol or Alkene?

→ Alcohol

Reagent: NaOH

Solvent: Aqueous (water present)

Conditions: Heat under reflux

Nucleophilic Substitution

→ Alkene

Reagent: KOH

Solvent: Ethanolic (no water)

Conditions: Heat under reflux

Elimination

Memory trick: Aqueous → Alcohol  |  Ethanolic → Elimination (both start with the same letter as the product/type)
2 · KMnO₄ with Alkene — Cold Dilute vs Hot Concentrated

→ Diol

KMnO₄: Dilute

Temp: Cold

Colour: Purple → colourless

Double bond intact (diol)

→ C=C Cleavage

KMnO₄: Concentrated

Temp: Hot

Products: Two carbonyl molecules

Double bond broken

Memory trick: Cold & dilute → gentle → keeps structure. Hot & conc. → harsh → destroys the C=C bond.
3 · Primary Alcohol Oxidation — Aldehyde or Carboxylic Acid?

→ Aldehyde

Reagent: K₂Cr₂O₇ / H₂SO₄

Method: Heat gently + distil immediately

Colour: Orange → green

Remove product before further oxidation

→ Carboxylic Acid

Reagent: K₂Cr₂O₇ / H₂SO₄ (excess)

Method: Heat under reflux

Colour: Orange → green

Keep product in flask for full oxidation

Key distinction: Same reagent, different procedure. Reflux keeps volatile aldehyde in flask → further oxidised. Distillation removes it → stopped at aldehyde.
4 · Reducing Carbonyls — NaBH₄ vs LiAlH₄

NaBH₄

Use for: Aldehydes & Ketones

Solvent: Aqueous

Safety: Mild, manageable

Aldehyde → 1° alcohol  |  Ketone → 2° alcohol

LiAlH₄

Use for: Carboxylic acids (+ amides, nitriles, esters)

Solvent: Dry ether (NO water)

Safety: Reacts violently with water

Carboxylic acid / nitrile → 1° alcohol / amine

Memory trick: NaBH₄ = Nice & mild. LiAlH₄ = Lethal around water — needs dry ether. LiAlH₄ is more powerful (reduces COOH, NaBH₄ cannot).
5 · Halogenoalkane + Nucleophile — Aqueous vs Ethanolic Solvent

Aqueous → OH⁻ wins

Nucleophile: OH⁻ (NaOH/aq)

Solvent: Water

Substitution → Alcohol

Ethanolic → Elimination favoured

Nucleophile: OH⁻ (KOH/ethanol)

Solvent: Ethanol (no water)

Elimination → Alkene

Also applies to CN⁻ and NH₃: must use ethanolic conditions to avoid water competing and giving an alcohol instead of the nitrile / amine.
6 · Alcohol Dehydration vs Ester Formation (both use acid + heat)

→ Alkene (dehydration)

Reactants: Alcohol only

Catalyst: Conc. H₂SO₄ or H₃PO₄

Conditions: Heat

Elimination — water lost

→ Ester (esterification)

Reactants: Alcohol + carboxylic acid

Catalyst: Conc. H₂SO₄

Conditions: Heat under reflux

Condensation — water lost + ester formed

Both lose water, but esterification requires a carboxylic acid as the second reactant. If only an alcohol is present → dehydration to alkene.

🧠 Memory Aids

Solvent Tells You the Product

Aqueous → Alcohol (substitution)

Ethanolic → Elimination (alkene) or nitrile / amine

The first letter of the solvent matches the first letter of the product type.

KMnO₄ — Temperature Decides

Cold + dilute → Gentle → Diol (adds OH groups)

Hot + conc. → Harsh → Splits the C=C completely

FRS — Three Steps to Remember

Initiation — UV splits X₂ → 2X•

Propagation — chain reaction (×2 steps)

Termination — two radicals combine

"I Prevent Trouble"

Alcohol Oxidation — Method Matters

Distil → stop at aldehyde (remove before further reaction)

Reflux → go all the way to carboxylic acid

Same reagent (K₂Cr₂O₇/H⁺) — procedure controls product.

Halide Reactivity Order

C–F  >  C–Cl  >  C–Br  >  C–I

Bond strength decreases ↓  →  Rate of reaction increases ↑

Iodo-compounds react fastest with nucleophiles (weakest C–X bond).

Testing for Functional Groups

Alkene: bromine water orange → colourless

Alkene (alt): acidic KMnO₄ purple → colourless

Alcohol: PCl₅ → misty white fumes of HCl

Halide speed: AgNO₃(aq) → Cl=white, Br=cream, I=yellow ppt