Aryl Halides

By:- Dr.Harpreet Kaur

PGGCG11 CHD
DEPARTMENT OF CHEMISTRY

Aryl Halides

Ar-X

Organic compounds with a halogen atom attached to an

aromatic carbon are very different from those compounds
where the halogen is attached to an aliphatic compound.
While the aliphatic compounds readily undergo
nucleophilic substitution and elimination reactions, the
aromatic compounds resist nucleophilic substitution, only
reacting under severe conditions or when strongly
electron withdrawing groups are present ortho/para to the
halogen.

Aryl halides, syntheses:

1. From diazonium salts
Ar-N2+ + CuCl Ar-Cl

Ar-N2+ + CuBr Ar-Br

Ar-N2+ + KI

Ar-I

Ar-N2+ + HBF4 Ar-F

2. Halogenation
Ar-H + X2, Lewis acid Ar-X + HX
X2 = Cl2, Br2
Lewis acid = FeCl3, AlCl3, BF3, Fe

reactions of alkyl halides

Ar-X

1. SN2

NR

2. E2

NR

3. organo metallic compounds

similar

4. reduction

similar

Ag+
-OH

-OR

aryl halide
NH3

C C X
vinyl halide

-CN

ArH
AlCl3

NO REACTION

Bond Lengths ()

CCl

CBr

CH3X

1.77

1.91

C2H5X

1.77

1.91

(CH3)3CX

1.80

1.92

CH2=CHX

1.69

1.86

C6H5X

1.69

1.86

sp3

sp2

In aryl halides, the carbon to which the halogen is attached

is sp2 hybrizided. The bond is stronger and shorter than the
carbon-halogen bond in aliphatic compounds where the
carbon is sp3 hybridized. Hence it is more difficult to break
this bond and aryl halides resist the typical nucleophilic
substitution reactions of alkyl halides.
The same is true of vinyl halides where the carbon is also
sp2 hybridized and not prone to nucleophilic substitution.
In a manner analogous to the phenols & alcohols, we have
the same functional group in the two families, aryl halides
and alkyl halides, but very different chemistries.

Aryl halides, reactions:

1. Formation of Grignard reagent
2. EAS
3. Nucleophilic aromatic substitution (bimolecular displacement)
(Ar must contain strongly electron withdrawing groups ortho
and/or para to X)
4. Nucleophilic aromatic substitution (elimination-addition)
(Ring not activated to bimolecular displacement)

1) Grignard reagent

Br

Mg
anhyd. Et2O
Mg

Cl

THF

MgBr

MgCl

2) EAS
The X group is electron-withdrawing and
deactivating in EAS, but is an ortho/para director.
Br

Br

Br
NO2
+

HNO3, H2SO4

NO2

Br
SO3H
+ Br

H2SO4,SO3

Br

SO3H

Br
Br

Br2,Fe

+
Br

Br
CH3CH2-Br, AlCl3

CH2CH3
+

Br

CH2CH3

3) Nucleophilic aromatic substitution (bimolecular

displacement)
Ar must contain strongly electron withdrawing groups
ortho and/or para to the X.
Cl

NH2
NO2

NO2
+ NH3

NO2

NO2

Br
O2N

O2N

NO2

OCH3
NO2

+ NaOCH3
NO2

NO2

Cl
+ NaOH

NR

OH
350oC, 4500 psi

H+

OH

Cl
15% NaOH, 160oC

H+

NO2

NO2

OH

Cl
O2N

NO2

NO2

warm water

O2N

NO2

NO2

NH2

Cl
NH3, Cu2O, 200oC, 900 psi

NH2

Cl
NO2

NH3, 170oC

NO2

NO2

NO2

NH3

Cl
O2N

NO2

NO2

NH3, room temp.

O2N

NO2

NO2

bimolecular displacement (nucleophilic aromatic substitution)

mechanism:

Z
1)

2)

RDS

X + :Z

Z
X

+ :X

Z
X

Z
X

Z
G
X

G
If G is an electron withdrawing group in the ortho and
para positions, it will stabilize the intermediate anion.

evidence for the bimolecular displacement mechanism:

no element effect : Ar-I Ar-Br Ar-Cl Ar-F
(the CX bond is not broken in the RDS)

4) Elimination-Addition, nucleophilic aromatic substitution.

When the ring is not activated to the bimolecular
displacement and the nucleophile is an extremely good
one.
NH2

Br
+ NaNH2, NH3

Li

F
+

Li

H2O

Elimination-Addition mechanism (nucleophilic aromatic

substitution)
X

X
H

+ :NH2

1)

+ NH3
elimination

+ :X

2)
benzyne

3)

NH2

+ :NH2
addition
H

:
4)

NH2

NH2
+ NH3

+ :NH2

While the concept of benzyne may appear to be strange,

there is much evidence that this mechanism is correct.
NH2

Cl
*

NaNH2

NH2

NH3
47%

* = 14C

53%

Br
H3C

OCH3

NaNH2

NR

NH3
Cl

Cl

D
+ :NH2

benzyne intermediate has been trapped in a Diels-Alder

condensation:

THANK YOU