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

X -OR

aryl halide NO REACTION

NH3

-CN
C C X
vinyl halide ArH
AlCl3
Bond Lengths (Å)

C—Cl C—Br
CH3—X 1.77 1.91
C2H5—X 1.77 1.91 sp3
(CH3)3C—X 1.80 1.92
CH2=CH—X 1.69 1.86
sp2
C6H5—X 1.69 1.86
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

Mg
Br MgBr
anhyd. Et2O

Mg
Cl MgCl
THF
2) EAS The –X group is electron-withdrawing and
deactivating in EAS, but is an ortho/para director.

Br Br Br
HNO3, H2SO4 NO2
+

Br NO2
SO3H
H2SO4,SO3
+ Br SO3H

Br Br
Br2,Fe Br
+

Br
Br
CH2CH3
CH3CH2-Br, AlCl3
+ 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 OCH3
O2N NO2 O2N NO2
+ NaOCH3

NO2 NO2
 Cl

+ NaOH NR

OH
350oC, 4500 psi H+

Cl OH
15% NaOH, 160oC H+

NO2 NO2

Cl OH
O2N NO2 O2N NO2
warm water

NO2 NO2
 Cl NH2
NH3, Cu2O, 200oC, 900 psi

Cl NH2
NO2 NH3, 170oC NO2

NO2 NO2

Cl NH3
O2N NO2 O2N NO2
NH3, room temp.

NO2 NO2
bimolecular displacement (nucleophilic aromatic substitution)
mechanism:

Z
1) X + :Z RDS
X

Z + :X
2) Z
X
 Z

Z Z Z

X X X

Z Z
G
X 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 C—X 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.
Br NH2

+ NaNH2, NH3

F Li
H2O
+ Li
Elimination-Addition mechanism (nucleophilic aromatic
substitution)
X X
H :
1) + :NH2 + NH3

elimination
X
:
2) + :X

benzyne

:
NH2
3) + :NH2

addition
H
NH2
:

NH2
4) + NH3 + :NH2
While the concept of “benzyne” may appear to be strange,
there is much evidence that this mechanism is correct.

Cl NH2
NaNH2 NH2
* * + *
NH3

* = 14C 47% 53%

Br
H3C OCH3 NaNH2
NR
NH3

Cl Cl
D H
+ :NH2
benzyne intermediate has been trapped in a Diels-Alder
condensation: