C-Cl bond is polar due to chlorines electronegative.

In this case, this is offset to some extent by the

movement of electrons back towards the ring in the delocalisation.
http://www.chemguide.co.uk/organicprops/arylhalides/background.html#top

Cl

O
CH3-C- O
CH3

OH
Azo group, stepping stone for
delocalized electrons

Nucleophilic substitution only under extreme

conditions due to enhanced polarity of C-Cl
compared to C-H bond in benzene
o
(Conditions NaOHaq 300 C and 300atm)

OH

N=N-

NaOH Catalyst

Phenyamine
aniline

nitrobenzene

NO2

electrophile
Conc nitric & conc
sulphuric
Reflux 55oC

Benzene diazonium chloride

Tin (Sn) & Conc

HCl
Reflux

Nitrous acid and

HCl (use NaNO2)
Below 10oC

room temp
dry inert solvent

electrophile

C6H5N2+Cl-

electrophile
Acyl chloride and
anhydrous aluminium
chloride AlCl3

Methylbenzene
Toluene

CH3

room temp
dry inert solvent

O
C - CH3

Enhanced reactivity with

aqueous Br2 when compared
with benzene
due to OH directing (No Catalyst
Required)
White ppt

Br

O
C O-

Br
NH2

(ether)

Br
iodoform
NaOH and I2

+ CHI3 yellow ppt

OH

Br

Br
CH(OH)CH3

Phenylethanone

Cl2 and anhydrous

aluminium chloride Fe
or FeCl3 or AlCl3

Cl2 and hv

reflux

CH3

O
C-H

CH2Cl
Cl

Reflux with KMnO4

O
C - OH
Reflux with KMnO4

Benzaldehyde

Phenoxide

NaOH
C6H6O- Na+ + H2O
Na
C6H6O- Na+ + H2
Carbonate no reaction

+ H2O C6H5OH + N2 + HCl

Enhanced reactivity with

aqueous Br2 when compared
with benzene
due to NH2 directing
White ppt

(ether)

+
+
+

Slightly acidic

C6H5NH2 + HNO2 + HCl C6H5N2+Cl- + 2H2O

CH3C+O

OH

Water
o
Warm above 10 C

C6H5NO2 + 6[H] C6H5NH2 + H2O

CH3+

phenol

N2+Cl-

NH2

C6H6 + HNO3 C6H5NO2 + H2O

Chloromethane and
anhydrous aluminium
chloride AlCl3

Electrophylic
Substitution

reflux
dry inert solvent (ether)

NO2+

Ester

NOT Carboxylic acid unless NaOH

BUT acyl chloride

Chlorine and anhydrous

aluminium chloride AlCl3
or Fe or FeCl3

Benzyl Alcohol
(Phenylethanol)

CH2 - OH

Benzoic Acid
Benzyl Alcohol
(Phenyl methanol)

Br
More acidic than
phenol due to
halogen

Enhanced reactivity with

aqueous HNO3 when compared
with benzene
due to OH directing
mixture of 2 and 4 nitrophenol

6
5

OH

2
NO2