Process (with Product (with name and

Compound reagents) position) Key point

Sulphonation Benzenesulphonic acid Reversible reaction, SO3H grou

Benzene (H2SO4) (SO3H at any position) activates ortho and para positio

Electrophilic aromatic substitu

Nitration Nitrobenzene (NO2 at any NO2 group deactivates ortho a
Benzene (HNO3/H2SO4) position) para positions

X can be Cl or Br, FeX3 is a Lew

Halogenation Halobenzene (X at any acid catalyst, X group deactiva
Benzene (X2/FeX3) position) ortho and para positions

Friedel-Crafts R can be any alkyl group, AlCl3

alkylation Alkylbenzene (R at any Lewis acid catalyst, R group
Benzene (RCl/AlCl3) position) activates ortho and para positio

RCO can be any acyl group, AlC

Friedel-Crafts is a Lewis acid catalyst, RCO gr
acylation Acylbenzene (RCO at any deactivates ortho and para
Benzene (RCOCl/AlCl3) position) positions

CH3 group activates ortho and

Sulphonation p-Toluenesulphonic acid para positions, but para is
Toluene (H2SO4) (SO3H at para position) preferred due to steric hindranc

CH3 group activates ortho and

Nitration o- and p-Nitrotoluene (NO2 para positions, but ortho is mo
Toluene (HNO3/H2SO4) at ortho or para position) reactive due to inductive effect

CH3 group activates ortho and

Halogenation o- and p-Halotoluene (X at para positions, but para is
Toluene (X2/FeX3) ortho or para position) preferred due to steric hindranc
 Process (with Product (with name and
Compound reagents) position) Key point

Friedel-Crafts CH3 group activates ortho and

alkylation o- and p-Alkyltoluene (R at para positions, but para is
Toluene (RCl/AlCl3) ortho or para position) preferred due to steric hindranc

Friedel-Crafts CH3 group activates ortho and

acylation o- and p-Acyltoluene (RCO para positions, but para is
Toluene (RCOCl/AlCl3) at ortho or para position) preferred due to steric hindranc

Process (with Product (with

Compound reagents) nomenclature) Key points

- Aniline is activated towards

electrophilic substitution due to
the lone pair on nitrogen. <br> -
Ortho- and para- The sulfonic acid group can be
Sulphonation: aminobenzenesulfonic removed by heating with dilute
Aniline H2SO4 (conc.) acids or NaOH.

- Aniline is nitrated at low

temperature to avoid oxidation
the amino group. <br> - The nit
group can be reduced to amino
Nitration: HNO3 + Ortho- and para- group by catalytic hydrogenatio
Aniline H2SO4 (cold) nitroanilines or Sn/HCl.

- Aniline reacts with halogens in

Halogenation: X2 + Ortho- and para-
Aniline FeX3 (X = Cl or Br) halogenoanilines
the presence of a Lewis acid
catalyst such as FeCl3 or FeBr3
<br> - The halogen atom can be
replaced by other groups such
OH, NH2, NO2 by nucleophilic
aromatic substitution.

Friedel-Crafts - Aniline reacts with acyl chlorid

acylation: in the presence of AlCl3 to form
Aniline CH3COCl + AlCl3 Ortho- and para-acetanilides amides. <br> - The acyl group c
 Process (with Product (with name and
Compound reagents) position) Key point

be hydrolyzed to carboxylic aci

heating with aqueous NaOH or
H2O/H+.

- Aniline reacts with alkyl halide

the presence of AlCl3 to form
Friedel-Crafts alkylamines. <br> - The alkyl gr
alkylation: CH3Cl + can be oxidized to carboxylic a
Aniline AlCl3 Ortho- and para-toluidines by KMnO4 or K2Cr2O7/H+.

- Chlorobenzene is deactivated
towards electrophilic substituti
due to the electron-withdrawing
effect of chlorine. <br> - The
Sulphonation: Ortho- and para- sulfonic acid group can be
H2SO4 (conc.) + chlorobenzenesulfonic removed by heating with dilute
Chlorobenzene SO3 acids or NaOH.

Nitration: HNO3 +
Chlorobenzene H2SO4 (hot)
- Chlorobenzene is nitrated at h
temperature to overcome its
deactivation effect. <br> - The n
group can be reduced to amino
Ortho- and para- group by catalytic hydrogenatio
nitrochlorobenzenes or Sn/HCl.

- Chlorobenzene reacts with

halogens in the presence of a
Lewis acid catalyst such as FeC
or FeBr3 or under UV light. <br>
Halogenation: X2 + Ortho- and para- The halogen atom can be repla
FeX3 (X = Cl or Br) dihalobenzenes or by other groups such as OH, NH
or X2 + UV light (X monohalobenzenes NO2 by nucleophilic aromatic
Chlorobenzene = Cl or F) (depending on conditions) substitution.

Friedel-Crafts - Chlorobenzene does not unde

acylation: Friedel-Crafts acylation due to
Chlorobenzene CH3COCl + AlCl3 No reaction deactivation effect of chlorine a
 Process (with Product (with name and
Compound reagents) position) Key point

the formation of a complex

between AlCl3 and chlorine.

- Chlorobenzene does not unde

Friedel-Crafts alkylation due to
Friedel-Crafts deactivation effect of chlorine a
alkylation: CH3Cl + the formation of a complex
Chlorobenzene AlCl3 No reaction between AlCl3 and chlorine.

- Nitrobenzene is strongly
deactivated towards electrophi
substitution due to the electron
withdrawing effect of the nitro
Sulphonation: group. <br> - The sulfonic acid
H2SO4 (conc.) + Ortho- and para- group can be removed by heati
Nitrobenzene SO3 nitrobenzenesulfonic acids with dilute HCl or NaOH.

- Nitrobenzene is nitrated at hig

temperature to overcome its
deactivation effect. <br> - The n
group can be reduced to amino
Nitration: HNO3 + Ortho- and para- group by catalytic hydrogenatio
Nitrobenzene H2SO4 (hot) dinitrobenzenes or Sn/HCl.

- Nitrobenzene reacts with

Halogenation: X2 + Ortho- and para-
Nitrobenzene FeX3 (X = Cl or Br) halonitrobenzenes
halogens in the presence of a
Lewis acid catalyst such as FeC
or FeBr3. <br> - The halogen at
can be replaced by other group
such as OH, NH2, NO2 by
nucleophilic aromatic substitut

- Nitrobenzene does not underg

Friedel-Crafts acylation due to
strong deactivation effect of th
Friedel-Crafts nitro group and the formation o
acylation: complex between AlCl3 and nit
Nitrobenzene CH3COCl + AlCl3 No reaction group.
 Process (with Product (with name and
Compound reagents) position) Key point

- Nitrobenzene does not underg

Friedel-Crafts alkylation due to
strong deactivation effect of th
Friedel-Crafts nitro group and the formation o
alkylation: CH3Cl + complex between AlCl3 and nit
Nitrobenzene AlCl3 No reaction group.

- Phenol is activated towards

electrophilic substitution due to
the resonance effect of the
Sulphonation: Ortho- and para- hydroxyl group. <br> - The sulfo
H2SO4 (conc.) or hydroxybenzenesulfonic acid group can be removed by
Phenol SO3 (fuming) acids heating with dilute HCl or NaOH

- Phenol is nitrated at low

concentration and temperature
avoid oxidation of the hydroxyl
Nitration: HNO3 + group. <br> - The nitro group ca
H2SO4 (dilute) or Ortho- and para- be reduced to amino group by
Phenol HNO3 (dilute) nitrophenols catalytic hydrogenation or Sn/H

- Phenol reacts with halogens i

2,4,6-trihalophenols or
Halogenation: X2 + monohalophenols
Phenol H2O (X = Cl or Br) (depending on conditions)
water to form trihalophenols or
monohalophenols depending o
the concentration and
temperature. <br> - The haloge
atom can be replaced by other
groups such as OH, NH2, NO2
nucleophilic aromatic substitut

- Phenol reacts with acyl chlorid

in the presence of AlCl3 to form
ketones. <br> - The acyl group
Friedel-Crafts be hydrolyzed to carboxylic aci
acylation: Ortho- and para- heating with aqueous NaOH or
Phenol CH3COCl + AlCl3 hydroxyacetophenones H2O/H+.
 Process (with Product (with name and
Compound reagents) position) Key point

- Phenol does not undergo Frie

Crafts alkylation due to the
Friedel-Crafts formation of a complex betwee
alkylation: CH3Cl + AlCl3 and hydroxyl group which
Phenol AlCl3 No reaction prevents further reaction.