Chemistry of Aryl Halides

Aryl Halides
Preparation:

1. Halogenation: 2. From Benzene Diazonium Chloride:

(A) Chlorination (A) Sandmeyer Reaction
(B) Bromination (For Chlorides & Bromides)
(C) Iodination (B) Action of KI
(For Iodides only)
_
(C) Balz-Schiemann Reaction
3. Hunsdiecker Reaction: (For Fluorides only)

4. Raschig Process (Commercial Process)

 &

ARYL HALIDES : X X : F Cl Br I
, , ,

Halo benzene 's

• Disubstituted aryl halides : =

( o
, p,
m
)
✗ ( F, Cl Br )
I

HAL
, ,
↳
G
-

M ,
-

(reverse
I
,
-
It

+ M, + I ,
+ H
( Deactivating hyperconjugation
( activating groups) groups)
eg.ca } ; CES
-

CH } ( + I/ + H ) -

X C- I > +M )
-09-13 ;
-
OH
j
-

MHz -

Noz ;
-
CHO
;
-
COOH
C- M / -
I)
( -
I < + M )
1. Halogenation: ( Direct )(ArSE or EAS ) (A) Chlorination
Cn benzene
) (B) Bromination
CI - CI (C) Iodination
A1U3 / Fed }
( Lewis Acid
) ft
+ HCl
>
Bvz / Fe BÑ
BVz/TeBV3 ( Bromonivm
for
IYAIU } Bhf cat cation 1- HBR

Not a
Bhf H2O
good
method BVz/CH3C00H
F- Eci "
T
T
I
1- HI + HCl
Along
( strongly) C- Atala )
R.tt
2. From Benzene Diazonium Chloride: ( Prepn)
Y°2 ,NHz ¥zCI
HN03(c) Sn NaN0z
HCl
42504¢ ) HCl
( Oc)
(Nitration) (Red ) "

di -
azotisation

7
↳

(A) Sandmeyer Reaction (For Chlorides & Bromides)

Ñz% -

cud
Cl + Nz 'T
HCl

(chlorobenzene)
(A) Sandmeyer Reaction (For Chlorides & Bromides)

Ñz% -

cud
Cl + NZT
HCl

(chlorobenzene)
Cer Br
Br + Nz 'T
H Br

( Bromo benzene)

Cucn
CN
(cyanobenzene)
HCN

Benzonitne
note : Iodo benzene
-
is not formed n' a Sande meyer
Reaction .
(B) Action of KI (For Iodides only)

É?a - KI
•
- I + Nz ?

(C) Balz-Schiemann Reaction (For Fluorides only)

1413-1-4
Ñzc ,
-

ÑzBFq
-
HCl

nBF4
☐
F + BFzTtNzT
↳ ooo benzene,

(
HCl

)
-

Bfz
-

-
Nz
 3. Hunsdiecker Reaction: (Free Radical )
0

AS " Bvz

Agco ,
→ Br
cooy
,
silver benzoate
0684 +
AgBv

4. Raschig Process (Commercial Process)

CI
(a) Click
+ HCl +
4202 d-, = Et LSE)
← moroni um ) (b)
ion
•
HCl 1- Yzoz µjc+, Hzo
A 450°C
÷←
-
H2O
qµ
"
OH
-
-
-

me , +
(Phenol)
treated
-

for (a)
 CHEMICAL PROPERTIES Of Aryl Halides

1. Nucleophilic Substitution Reactions

(A) Under Abnormal Conditions
(B) Under Special Conditions
2. Free Radical Substitution
(a) Fittig Reaction (b) Wurtz-Fittig Reaction (c) Ullmann Reaction
3. Reduction
4. Reaction with Metals (Organo-metallics)
5. Formation of DDT
6. Electrophilic Substitution
1. Nucleophilic Substitution Reactions
(A) Under Abnormal Conditions (B) Under Special Conditions
Aryl halides do not SN reactions under
give
normal conditions ( usually given readily by
Alkyl halides
why ? )
Observe :
-
Foo
✗ •
Bond formed by
q

lp ✗ atom
spa - c
§ -

c -

p orbital
of ✗
)
• over is in
conjugation
with Fe's of ring = Resonance forms a
stronger
bond unlike in

9€ alkyl
① halide
¥ <→ . . .
.
So not broken easily
by a
Nucleophile .

- - - .
.e→ - . . - <→
! !
visualise Resonance hybrid of an Aryl halide !!
8- •+ '

between C' atom

÷: ✗ bond
of ring
- - - -

a
or -
& ✗ -

atom is Partial covalent

stronger ←
bond
[C ×
]
bond ( stable)
Nucleophile can't break this

partial double bond . ~~ Path -

I

Note : •
Also observe ✗ -
C does not have a

strong electrophilic character ( ?)

•
Note that ✗ -
C & X -
atom bond can't
break to
form ( heterolyhcally) phenyl
carbocation as it is unstable ~_ Path I -
(a) SN under abnormal conditions :

OH
a0Haq
CI 350°C ; Cu salt
zooatm
( Dow's
H2O
)
process

450°C (Raschig 's process)

↳ Nao Haq
NHZ
⇐ 5°C) Nitz ; Cuzo

200°C 50 atm
(Dow's
,

N0R ? ? Reaction

Cuen CN
> (benzo
pyridine
-

nitrile)
250°C
5N under special conditions : (Designer Rxn
)
4) Using strong bases :
( NaN Hz ; KNHZ )
NHZ
1- KNHZ

( base) low
Temp 20°C (aniline)
€ (NU -
Elimn,
?
ÑHZ
\
H
# Nitz Benzyne
× ( an intermediate
- -

P + ÑH }
-02
unstable !!
✓ ( Nu addn)
-
-
ÑH - H
,

SN E. Nu -
Elim + Nu -

Addy NHZ
aniline
 Ii) Introducing deactivating groups( such Nose as -

in
% positions of Aryl Halides -5034) : or

I Naotlaar
Rxn
No .

Obviously °

€t¥×
> QOM
on

Noz
•
N°2 SN Rih
4,0
occurs !!
0 -
nitro halo benzene OH

QOH
SN Rxn
420
occurs
!)
Noz
.

Noz
Effect of deactivating group
:
by putting up
deactivating groups f- Noa ; -

sozh ) at

Yp positions has activated an aryl halide

towards SN Reaction = Activated SN Rxn
Observe :
reactivity of a Nu in a → →

CI
91 CI CI
Noz

④ < 17
E-
<
I
< 0
( Itm)
-

Noz
Noa
C- I weak)
C- M)
CI
CI
. - . .
4
N°2
§ 02N -

to -
Noz

I
Noz Noz
 ° "
H
02N Noz
NaOH
02N N°2
Picnic Acid
H2O
⇐ NP)
Noz
Noz Tri -
nitro
phenol
HNOZ (c)
42504¢ , ]
-

excess (strong
Pka
Acid)

~ 1.01
CI
2. Free Radical Substitution
(a). Fittig Reaction (b). Wurtz-Fittig Reaction (c). Ullmann Reaction

a cis D. E
Cl

Cdryethev
Fittig Rxn Biphenyl
RCI
visualise Cross -

product
Na/ D. E
Wurtz -

Fittig 2 ( alkyl benzene )

cults
D. E
( Ullmann's Rxn)
Biphenyl
I
Na / D. E
m← y-☐0- Me

CzH5-I
Me
me -0cg -

GHS

Na/ D. E

Calo me -⑦--Me
NaOH
No SN Rxn in aryl halide
H2O •
1 .

MHz
u
KNHZ

0°C
[⑦ ÑHZ : As
(
base
n' a
benzine)
nne
Patb
?⃝
3. Reduction
Al alloy
5¥16
Ni -

NO 1- HX
Rxn
?
RA
Naoto benzene
HI
usually not used .

Q :
why LIAI Hot can't be used ??
4. Reaction with Metals (Organo-metallics)
Li
Li = Phli
Mezo (dry) Phenyl lithium
×
Mg / THF
MGH
or Mezo (dry
) Grignard
Li reagent
(
1

)
.

2.
Cali =
cux
2 Phzculi
Gilmann's Reagent
5. Formation of DDT

Cl t Clzc -
§ -
µ
42504 (c)

(chloral )

(1) ichloro diphenyl CI -

:
C -
C -

Clz
Trichloroethane) (insectile)
6. Electrophilic Substitution (G)
Cl

: =
-
I
effect
= + in
effect
 Note : -
I > + M as a result all
,

halogen atoms are

weakly Deactiving
Note : Due to 1-+9 effect ; groups
✗ -
atoms are
weakly towards SE Rxns .

Xp -

directing
observe the increasing ease
of SE Rxns :

COOH Cl H
Noz Cltz OH
'

< < < < <

C-I > + M) effect 1-1=1+4 -1M > I

-

( m) C- M) No

Increasing ease ( Activating

•

o→
for
influence
SE Rin
forSEn)
 IMPORTANT Electrophiles/ SE Reactions : -

( Electrophiles)
Nitration
1 . ; HNO } Gone)
= Ñoz
cong
2.
Sulphonation :
50%2504 = 503

3. Bromination ; Brz / Fe or Hzo = BÑ

Frieda / craft Acylation c=É

R£÷g
4 : = R -

Acylium job

Alkylation
¥¥ Rt
5. F. C. : =
IMP : F
,
Cl
,
Br, I j all are
xp
-

directing
A mixture of o &
p product
1 .

2.

Br
3 .

4.

5-
 Aryl Halides | Memory Map
Reactions

1. Li NaOH (c)
CuLi OH
2 2. CuX 350°C, 200 atm

Mg NH3
MgX NH2
THF 200°C, 50 atm

Li CuCN
Li CN
D.E 250°C, Pyridine

Ni-Al NaNH2/NH3
NH2
NaOH, ! "33°C

X
+
E
SE Reaction
X X RX
Na, D.E
R
(P)
E Aryl Halide
X
X
E E+
SE Na, D.E
(O)

Nu

1. HNO3 Cu
H2SO4 !
(P)
2. Nu"
NO2

Nu 1. HNO3
H2SO4 Cl3C " CHO Cl
NO2
CHCCl3
2. Nu H2SO4
Cl
(O) DDT
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓