BENZENE

Halogenation

Equation: C​6​H​6​ + X​2​ → C​6​H​5​X + HX

Reagent: dry Cl​2​ gas, pure Br​2​ liquid
Condition: rtp
Catalyst: AlCl​3​ or FeBr​3​ (halogen carriers)

Generating electrophile: catalyst + X​2​ → [catalyst]​-​ + X​-

Nitration

Equation: C​6​H​6​ + H​2​SO​4​/HNO​3​ → C​6​H​5​NO​2​ + H​2​SO​4​ + H​2​O

Reagent: conc HNO​3​, conc H​2​SO​4​ (nitrating mixture)
Condition: 40-60​o​ under reflux
Catalyst: H​2​SO​4

Generating electrophile: 2H​2​SO​4​ + HNO​3​ → 2HSO​4​-​ + NO​2​+​ + H​3​O​+

Alkylation / Acylation

Equation: C​6​H​6​ + RCl/RCOCl → C​6​H​5​R / C​6​H​5​RCO + HCl

Reagent: alkyl halide (RCl) / acyl chloride (RCOCl)
Condition: heat under reflux
Catalyst: anhydrous AlCl​3

Generating electrophile: AlCl​3​ + RCl/RCOCl → [AlCl​4​]​+​ + R​+​ / RCO​-

Electrophilic addition

Hydrogenation

Equation: C​6​H​6​ + 3H​2​ → C​6​H​12

Reagent: hydrogen gas (H​2​)
Condition: 150​o​ temperature
Catalyst: nickel

Reactions of the side-chain

Free-radical substitution

Equation: C​6​H​5​CH​3​ + Cl​2​ → C​6​H​5​CH​2​Cl + HCl

Reagent: Cl​2
Condition: UV light

Notes: with an excess of Cl​2,​ we can obtain a mixture of di and tri chloromethyl benzene.
 ● When we halogenate methylbenzene (or any other alkylarenes), the halogen atom substitutes
into the benzene ring at positions 2 and 4.
● This is because the alkyl group is a ring-activating group (donates electrons to the ring), which
opens up positions 2 and 4.
● Two products can be formed: 2-chloromethylbenzene and 4-chloromethylbenzene.
● The carbon-halogen bond is stronger than a normal halogenoalkane bond, as the lone pair of
electrons on the halogen overlaps with the ring, and thus gives the CX bond a somewhat
double-bond character.

Oxidation

Equation: C​6​H​5​CH​3​ + 3[O] → C​6​H​5​COOH + 2H​2​O

Reagent: KMnO​4​ or K​2​Cr​2​O​7
Condition: heat with reflux

Notes: the alkyl group is always oxidised, regardless of the length of the chain. If there are more than
one alkyl groups, each one is oxidised.

HALOARENES

Nucleophilic Substitution

Equation: C​6​H​5​Cl + NaOH → C​6​H​5​OH + NaCl

Reagent: NaOH
Condition: 300 - 330​o​C, 150-300 atm

Ease of hydrolysis:
F > Cl > Br > I (down group, gets faster)

PHENOL

Neutralisation

Equation: C​6​H​5​OH + NaOH → C​6​H​5​O​-​Na​+​ + H​2​O

Reagent: NaOH
Condition: r.t.p

Regenerating phenol:
● When a strong acid (HCl) is added to a solution of sodium phenoxide, phenol is regenerated.

Metal + Acid

Equation: C​6​H​5​OH + Na → C​6​H​5​O​-​Na​+​ + ½ H​2

Reagent: Na metal
Condition: r.t.p

Notes:
● Because phenol does not react with metal carbonate to liberate CO​2​ it is a relatively weaker
acid than other carboxylic acids.
Electrophilic substitution: Bromination

Equation:

Reagent: Bromine (aq)

Condition: r.t.p

Notes:
● Rapid reaction, forms white ppt
● No catalyst required since the Br​2​ molecule is easily polarised

Electrophilic substitution: nitration

Equation:

Reagent: dilute HNO​3

Condition: r.t.p

CARBOXYLIC ACIDS

Oxidation

Tollen’s Reagent (methanoic acid)

Equation: HCOOH + [O] → CO​2​ + H​2​O

Reagent: Tollen’s
Condition: warm
Observations: silver mirror formed (Ag​+​ gets reduced to silver atoms)

Fehling’s Reagent (methanoic acid)

Equation: HCOOH + [O] → CO​2​ + H​2​O

Reagent: Fehling’s solution (very similar to benedict’s)
Condition: warm
Observations: red precipitate
Warm Acidified Manganate (KMnO​4​/H​+​) (ethanedioic acid)

HOOC-COOH + [O] → CO​2​ + H​2​O

Reagent: KMnO​4​ / H​+
Condition: warm, acidified
Observations: orange to green

ACYL CHLORIDES

Formation

With phosphorous (V) chloride

Equation: CH​3​COOH + PCl​5​ → CH​3​COCl + POCl​3​ + HCl

With phosphorous (III) chloride

Equation: 3CH​3​COOH​ +​ PCl​3​ → 3CH​3​COCl + H​3​PO​4

Condition: heat

With sulfur dichloride oxide

Equation: CH​3​COOH + SOCl​2​ → CH​3​COCl + SO​2​ + HCl

Hydrolysis

Equation: CH​3​CH​2​COCl + H​2​O → CH​3​CH​2​COOH + HCl

● Lone pair on oxygen from water initates attack on carbonyl carbon.

● This produces a carboxylic acid and HCl

With ammonia

Equation: R-CO-Cl + NH​3​ → R-CO-NH​2​ + HCl

Reagent: ammonia
Product: primary amide

● The HCl may be neutralised to form NH​4​Cl

With primary amides

Equation: R-CO-Cl + R’NH​2​ → R-CO-NHR’ + HCl

Reagent: alkylamine (primary amide)
Product: secondary amide

With alcohols and phenols

Equation: R-CO-Cl + HO-R → R-CO-OR + HCl
Reagent: alcohol at r.t.p, phenol dissolved in NaOH
Condition: phenol in NaOH should be warmed
Product: ester

AMINES

Nucleophilic substitution with ammonia and halogenoalkanes

Equation: CH​3​CH​2​Br + NH​3​ → CH​3​CH​2​NH​2​ + HBr

Reagent: ammonia
Condition: excess, hot alcoholic ammonia

Notes:
● HBr is removed by excess NH​3​ to form NH​4​Br

Halogenoalkane + CN​-

Equation: CH​3​Br + CN​-​ → CH​3​CN + Br​-

Reagent: KCN in alcohol
Condition: heat under reflux

This reaction forms ethanenitrile. We can make ethylamine by reducing ethanenitrile with a LiAlH​4​ in
dry ether.

Equation: CH​3​CN + 4[H] → CH​3​CH​2​NH​2

Reagent: LiAlH​4​ in dry ether, passing nitrile vapour and hydrogen gas over Ni catalyst.
Condition: Ni catalyst

Reducing amides to form amines

Equation: CH​3​CONH​2​ + 4[H] → CH​3​CH​3​NH​2​ + H​2​O

Reagent: LiAlH​4

Reducing nitrobenzene

Equation: C​6​H​5​NO​2​ + 6[H] → CH​3​CH​2​NH​2​ + H​2​O

Reagent: nitrobenzene
Condition: heat nitrobenzene with Sn catalyst and HCl
Reactions of phenylamine

Electrophilic substitution (bromination)

Equation: C​6​H​5​NH​2​ + 3Br​2​ → 2,4,6-TRIBROMOPHENYLAMINE + 3HBr

Reagent: aqueous bromine
Condition: r.t.p
Observations: white precipitate

Diazotization reaction

Equation:

Reagent: nitrous acid (NaNO​2​ with excess HCl)

● HNO​2​ is a weak, unstable acid, so we make it in situ with NaNO​2​ and HCl)
Condition: low temperature (<10​o​)

Notes
● Diazonium salts of arylamine are stabilised by the delocalisation of N’s electrons over the
benzene ring.
● The diazonium salt, however, is very unstable and can decompose at temps above 10​o​C to

Coupling reactions of diazonium salts

Electrophilic substitution

Equation:
Reagent: aromatic amines or phenols

● Positively charged diazonium ion acts as an electrophile, and substitutes into the benzene ring
of phenol at position 4.
● The delocalisied electrons extend between the two benzene rings through the NN group,
which acts like a bridge, and forms an azo dye.
● This makes the azo dye very stable.
● By using a variety of different aryl compounds (not just phenol) we can form a number of
brightly coloured dyes.

Formation of peptides

Primary amides

Equation: R-CO-Cl + NH​3​ → R-CO-NH​2​ + HCl

Reagent: conc NH​3
Condition: r.t.p

Secondary amides

Equation: R-CO-Cl + R’NH​2​ → R-CO-NHR’ + HCl

Reagent: conc NH​3
Condition: r.t.p

Reactions of amides

Reduction of amides

Equation: CH​3​CONH​2​ + 4[H] → CH​3​CH​3​NH​2​ + H​2​O

Reagent: LiAlH​4

Hydrolysis

Equation:
Reagent: either HCl or NaOH
Condition: heat under reflux