Benzene and derivatives

Chapter 25
Overview
• state the type of mechanism
• state the type of reaction
• state reagents and conditions needed for the reaction
• state expected observation of the reaction
• state bond angles

• deduce functional group based on observation

• draw structures
• draw isomers
• draw mechanisms

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One way to look at the chapter:
benzene vs phenol
1. Shape and bonding OH
2. Properties
3. Benzene
• Reactions of benzene
1. Electrophilic substitution
2. Electrophilic addition / hydrogenation
3. Alkylarenes: Oxidation
4. Alkylarenes: Free radical substitution
4. Phenol
1. Synthesis
2. Reactions: electrophilic substitution and acid-base reactions
3. Acid properties
4. Tests for phenol

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Another way to look at the chapter:
benzene ring vs side chain
1. Shape and bonding H H
2. Properties H H
O
3. Reactions on the benzene ring
1. Electrophilic substitution
2. Electrophilic addition / hydrogenation
4. Reactions on the side chain/substituent
1. Alkylarenes: Oxidation
2. Alkylarenes: Free radical substitution
5. Phenol
1. Synthesis
2. Reactions: acid-base reactions
3. Acid properties
4. Tests for phenol

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Recap: AS organic chemistry
• What are the bond angles around a carbon atom which is sp2
hybridized?

• How many electrons are involved in a pi bond?

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Recap: AS organic chemistry
Describe the reaction mechanism when HBr reacts with ethene,
CH2=CH2

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Recap: AS organic chemistry
Describe the reaction mechanism when:
(i) chloroethane reacts with NaOH

(ii) 2-chloro-2-methylpropane reacts with HCN

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Naming aromatic compounds
CH3 Cl NO 2 NH2 OH

NO 2 OH
CH2Cl COOH
Br Br NH2 O 2N NO 2

Br Br

Br NO 2

Br
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Shape and bonding in benzene, C6H6
• Shape: H
• Carbon atoms are sp2 hybridized H C H
• C-C-C bond angle of 120o – trigonal planar C C
• Benzene molecule has a planar structure C C
H C H
• Bonding:
• sp2 orbitals between C-H and C-C overlap to form 3 σ H
bonds per C atom
• p orbitals from each carbon atom overlap sideways
with each other forming π bonds
• The π bonds contain delocalized electrons →
resonance structures
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Resonance structure in benzene
H NO 2

NO2+ +

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Properties of benzene
• Clear, colourless, non-polar liquid at r.t.p
• Volatile and has a low b.p.
• Relatively unreactive due to strong bonding – catalyst required

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Reactions involving benzene and its derivatives

• Electrophilic substitution
• Halogenation
• Alkylation
• Acylation
• Nitration
• Reaction mechanism
• Hydrogenation
• Reactions to side chain:
• Oxidation
• Free radical substitution

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Electrophilic substitution: halogenation
• A hydrogen atom on an organic compound is replaced with one
halogen group.
Cl
anhydrous AlCl3 catalyst
+ Cl Cl
heat
+ HCl

Br
anhydrous AlBr3 catalyst
+ Br Br
heat
+ HBr

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Electrophilic substitution: alkylation
• A hydrogen atom on an organic compound is replaced with one
alkyl group.

CH3
anhydrous AlCl3 catalyst
+ CH3 Cl + HCl
heat

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Electrophilic substitution: acylation
• A hydrogen atom on an organic compound is replaced with one acyl
group.

O
O
anhydrous AlCl3 catalyst CH3
+ Cl CH3
+ HCl
heat

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Electrophilic substitution: nitration
• A hydrogen atom on an organic compound is replaced with one
nitro (-NO2) group.

conc. HNO3, conc. H2SO4 NO 2

+ HNO 3 + H2O
25 - 60 oC

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Summary of reagents and conditions:
Electrophilic Substitution
Reaction Electrophile Reagents Conditions

halogen gas bubbled heat, anhydrous AlX3

Halogenation halogen ion, X+
through benzene catalyst

heat, anhydrous AlX3

Alkylation R+ (where R = alkyl) halogenoalkane
catalyst

heat, anhydrous AlX3

Acylation RCO+ (where R = alkyl) acyl halide
catalyst

conc. HNO3
25-60 °C, conc. H2SO4
Nitration nitronium ion, NO2+ (if reacting with phenol:
catalyst
dil. or conc. HNO3)

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Electrophilic Substitution Mechanism
• Step 1: Generation of the electrophile

• Step 2: Electrophilic substitution by electrophile to form a

carbocation intermediate (slow step)

• Step 3: Deprotonation to restore aromaticity and regeneration of

catalyst (fast step)

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Electrophilic Substitution Mechanism: Halogenation

• Step 1:
Br-Br + AlBr3 → Br+ + [AlBr4]-

• Step 2 & 3:
Br
H Br
+
Br
+ + +
H

H+ + AlBr4- → HBr + AlBr3

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Electrophilic Substitution Mechanism: Alkylation

• Step 1:
CH3-C𝑙 + AlC𝑙 3 → CH3+ + [AlC𝑙 4]-

• Step 2 & 3:
CH3
H CH3
CH3+
+ + +
H

H+ + AlC𝑙 4- → HC𝑙 + AlC𝑙 3

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Electrophilic Substitution Mechanism: Acylation

• Step 1:
CH3CO-C𝑙 + AlC𝑙 3 → CH3CO+ + [AlC𝑙 4]-

• Step 2 & 3:
COCH 3
H COCH 3
+
COCH3
+ + +
H

H+ + AlC𝑙 4- → HC𝑙 + AlC𝑙 3

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Electrophilic Substitution Mechanism: Nitration

• Step 1:
HNO3 + H2SO4 → NO2+ + HSO4- + H2O (H-OH)

• Step 2 & 3:
NO 2
H NO 2
+
NO 2

+ + +
H

H+ + HSO4- → H2SO4
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Reactions of phenol

• Phenol is more reactive than benzene

• the oxygen atom's lone pair is delocalised into the ring system → increases
the electron density around the ring

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Reactions of phenol

1. Phenol + aqueous Br2

OH OH
Br Br

+ 3 Br Br + 3 HBr

Br
2,4,6-tribromophenol (white ppt)

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Reactions of phenol

2. Phenol + dilute nitric acid

OH OH OH
NO 2

+ 2HNO3 + + 2H2O

NO 2

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Reactions of phenol

3. Phenol + concentrated nitric acid

OH OH
O 2N NO 2

+ 3HNO3 + 3H2O

NO 2
2,4,6-trinitrophenol

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Reactions involving benzene and its derivatives

• Electrophilic substitution
• Halogenation
• Alkylation
• Acylation
• Nitration
• Reaction mechanism
• Hydrogenation
• Reactions to side chain:
• Oxidation
• Free radical substitution

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Hydrogenation of benzene
• Reagent: Hydrogen gas
• Conditions: Ni or Pt catalyst, heat

CH3 CH3

heat, Ni or Pt
+ 3H2

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Side Chain reactions
• Alkylarenes: Oxidation

CH3 COOH
1. alkaline KMnO4, reflux
2. dil. H2SO4
+ 3[O] + H2O

*Alkyl group always oxidized regardless of chain length

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Side Chain reactions
• Alkylarenes: Halogenation

CH3 CH2Cl

boil / UV light
+ Cl2 + HCl

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Reactions involving benzene and its derivatives

• Electrophilic substitution
• Halogenation
• Alkylation
• Acylation
• Nitration
• Reaction mechanism
• Hydrogenation
• Reactions to side chain:
• Oxidation
• Free radical substitution

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Ring activating/deactivating groups
• Side groups attached to benzene will influence which H atom is
substituted
• Ring activating: Alkyls, -Cl, -OH, -NH2 Compare and contrast:
halide substituents are
• Donates e- to the ring electron-withdrawing in
• +ve inductive effect (or delocalization of lone pair) straight-chain molecules
(negative inductive effect)
• Substitution occurs at position 2, 4 and/or 6
• Ring deactivating: -COR, -CHO, -COOH, -NO2
• Withdraws e- from ring
• -ve inductive effect
• Substitution occurs at position 3 and/or 5

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Phenol
Synthesis and acid properties
Tests for phenol
Acid properties of phenol

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Synthesis of phenol
dil. HCl
NaNO2 + HCl HNO2 + NaCl
nitric(III) acid

< 10oC + -
NH2 + HNO2 + HCl N NCl + 2H2O

benzenediazonium chloride /
phenylamine
(diazonium salt)

+ - warm
N NCl + H2O OH + HCl + N2

benzenediazonium chloride /
phenol
(diazonium salt)

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 < 10oC
Reactions of the benzenediazonium ion
+ -
+NH2 HNO2 + HCl + 2H2O N NCl

(will be revisited in C27)

+ - warm
N NCl + H2O OH + HCl + N2

benzenediazonium
phenol
chloride
(diazonium salt)

benzenediazonium benzene-
chloride containing
(diazonium salt) compound azo dye

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Acidity of phenol
• Ethanol does not show acidic properties, but phenol does.
• The acid strength of a compound depends on its ease in donating protons
• The strength of the bond being broken
• The stability of the conjugate base formed
→ Increasing acidity →
Ethanol Water Phenol

CH3 is electron donating so O-H bond is O-H bond weakened by negative

stronger inductive effect of benzene ring

A less stable ethoxide ion is formed as A more stable phenoxide ion is formed as
the negative charge is concentrated on the negative charge is spread out over
the oxygen atom the whole ion

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Phenol: acid-base and metal-acid reactions

- +
OH + NaOH O Na + H2O

- +
2 OH + 2Na 2 O Na + H2

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Test for phenol (recap)
• Reagent: bromine water (Br2(aq)) – orange
• Observation: white ppt. formed (2,4,6-tribromophenol)
Br

OH + 3Br2 Br OH + 3HBr

Br

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Reaction of phenylamine
• Reagent: bromine water (Br2(aq)) – orange
• Observation: white ppt. formed (2,4,6-tribromophenylamine)
Br

NH2 + 3Br2 Br NH2 + 3HBr

Br

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Phenol and chlorobenzene:
unreactive at the C-OH and C-Cl bond

–O–H – C𝑙
unreactive unreactive

C-O bond in phenol C-Cl bond in chlorobenzene

1. p-orbital in O overlaps with π- 1. p-orbital in Cl overlaps with π-
electron cloud electron cloud
2. lone pair of e- in O delocalises into 2. lone pair of e- in Cl delocalises into
ring ring
Outcome C-O bond is stronger in phenol C-Cl bond is stronger in chlorobenzene

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Nitration of phenol (recap)
OH OH OH
NO 2

+ dil. HNO 3 +

NO 2

OH OH
O 2N NO 2

+ conc. HNO 3

Phenol can react with HNO3

under mild conditions
NO 2 (contrast with benzene)

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