Preparation of Alkyl
Halide
From Alcohol
A) Action (✗ ≠ F)
By of tix
Rote 1- HX → RX + H2O
Substrate
Reagent Alkyl Halide
Leaving Group
Role
of HX ?
is
Leaving Group
_
OH a
poor .
-1
So we use It to convert on to H2O and
is
good leaving
H2o a
group
.
P block C̲ i ̲r ̲c̲l ̲e̲
- -
ROH + × → RX + OH ✗ Not Possible
leaving group
is
-
very
on
poor .
strong Bases
leaving Group
◦
are poor -
weak Base are
good leaving group
.
:
Visualise Rxn
ROH + HX → RX + 1-120
lag )
-
⊕
R -
✗ → R -
OH → Hao + Rt
te carbocation
Rearrange if
required
P block C̲ i ̲r ̲c̲l ̲e̲
Rt →
-
+ × R -
✗
Chile: a) CH CH CH } CH3 CH CHS
-
-1
- -
z
-
I ⊕
,
:0H
C. 1-13 -
CH -
CH
}
1
Bee
CH3 CH3
1 I
b) CH } -
CH -
CH -
CH z
# ctlz
-
CH -
CH
-
CH
}
I ⊕
OH
1,1-1
2° -
shift
FH3 443
CH 2-
CI-13 C cuz CHG CH3
- -
- -
±
P block C̲ i ̲r ̲c̲l ̲e̲
c)
"
€,
É→
EEE
⑦
+2
"
d)
OH
H -
Revise>cpaÑ
5
6
carbocation
Range
in
ÉI ◦
P block C̲ i ̲r ̲c̲l ̲e̲
Ease 3° 2° 1°
of Reaction : > >
ROH 8 3%011 > 2 Tron > Tron
HX : HI 7 H Bee > HCl
ii )
ROH + Na Br + Hzsoy -7 R Br + Natl soy -11420
Mainly for 1° → HBu
iii ) 12011 + Na I + 1131004 d- RI +
Nazpoy + H2O
C ,
with
we can't use Hzsoy Nat or Kl because HZSOY
Oxidase NAI to Iz .
P block C̲ i ̲r ̲c̲l ̲e̲
Pcl -5 Rct + POC 13 + HCl
04
"
Pclz P
RCI +
1-131>03 ou
-
of
ROH
sock (
Rcs + soz HCl
Prefferrd )
+
-
Gases will escape
(¥+c
Sociz Rct +
502 +
,
Pyridine
☆
1%1
P block
◦ ◦
-
C̲ i ̲r ̲c̲l ̲e̲
Lucas Test ( for Preparation chlorides)
Mainly of
Znc / 2
ROH + HCl > Rct + H2O
Znclz is used as a
catalyst
RÉnciz → r
-1£Is -
zinc , ≥
_ÉÉÉÉoñ%]
PROH
.li#iVZnC1ztH2O-R-c1
Ease
=
8
3,020,1 >
272011 >
P block C̲ i ̲r ̲c̲l ̲e̲
Lucas Test : Distinction between 1° ,
2° ,
3° Alcohol
ROH 1- Hcl RCI + H2O
-
Turbidity
Observation 8
if solution
of RCI in H2O turns
( Turbid ) white
Milky or
give a
Turbidity instantly -
It means ROH is 3°
Observation if turbidity after
gap of
:
appear a
3- 5 mins then It means Alcohol
,
is 2° .
P block C̲ i ̲r ̲c̲l ̲e̲
Observation Temp ,
:
If there is no
turbidity at Room
ROH is 1° .
heating formation 1°C -1
On
, of is
possible
.
In this case
,
white
Turbidity appear
on
heating .
P block C̲ i ̲r ̲c̲l ̲e̲
Reaction
Halogen Exchange
:
a) Finkelstein Reaction ( For Iodides )
Acetone
RX + NAI > RI + Naxt ,
X-Br
R -
CI + Naz €É RI + NaCl ↓
Precipitate
D@vingFoxeofRxn.E
.
1° 2° 3°
of Rxn 8 #
ase > > so Ren moves
,
← in Forward Drrecn
P block C̲ i ̲r ̲c̲l ̲e̲
Eee .
HI
y A ( Markovnikov Addn
Anti -
Man .
HBr NAI
y B y c
Peroxide Acetone
Na I
NBS ,
s ☐ > E
y Acetone
F
ccly
A : D:
I
\
Bee
B : C ?
, 1
Bee I E- % \
,
P block I
C̲ i ̲r ̲c̲l ̲e̲
b) Swarts Reaction ( For Fluorides)
→
RX + Metal Fluoride RF + Metal Handed,
R= Cl ,
Bee ,
I
Metal Fluorides 8
Agt , 1-1921=2 ,
C. 01=3
RCI R F
Agf
+ + ↓
Age
→ -
RCI
Hgzfz R
Hgzclzt
t → -
F T
Bee F
HBO
AGF 1
Peroxide
P block C̲ i ̲r ̲c̲l ̲e̲
→ Hunsdieckeee Reaction ( mainly for Bromide)
From carboxylic Acid
Silver Salt
of
R-É-o-A
0
R É OH + →
Agon
- -
Ii
R Baz R Br
Ag
C +
179138
- -
O - -
+ coz +
( step down Rxn)
É "
+
Ag Beez
AgBr
o CO2 ←
ctez CH3Br +
- - -
P block C̲ i ̲r ̲c̲l ̲e̲
Hickson : ( Free Radical Path )
R É + Baz R É 00 NO
Boi :
Ag
A-
gBee
- -
o - -
-
o -
+
µ 00
lp -
lp Repulsion
is cause
of homolytrc
Bond
Breaking
i
R -
C
-
G + Bie
12° +
coz 't \
12° + Bu° → R -
Ba
P block C̲ i ̲r ̲c̲l ̲e̲
Preparation of RX
Swanston Finkelstein ( iodide)
ROH 1-
Alkane
Halogenation of
PCI
-51pct 3/5042
-
tlunsdiecker Rxn
( Bromide]
Lucas
> R ✗
( chloride )
T Alkene + HX
( Markovnikov
ROH -1 Nat Alkene -1 HBO / Peroxide
Hzpoy Anti - Marko nekov
ROH + Nats Alcohol + Allylic Brominn ( NBS)
-
HX
112504 42 ( 50202
P block
Allylic
a)
C̲ i ̲r ̲c̲l ̲e̲
Physical Properties :
Physical state a) Physical state
Point
Boiling
◦
Point
c '
Cy 8 Gases
melting
-
Cs
◦
Solubility Co 8
Liquids
-
8 solids
◦
Density Cq - - _ .
◦
Dipole Moment
As Size Increases ,
Vanderwaal
forces Increases ,
Physical
state
changes
.
P block C̲ i ̲r ̲c̲l ̲e̲
b)
Boiling
Point ✗
strength of Intermolecular forces
R ✗
Hydrocarbon Halide
Part
Intermolecular Forces ✗
Polarity
✗ Vanderwaal Forces ✗ Molar Mass
Forces 1-
Vanderwaal ✗
Surface area ✗
Branching .
P block C̲ i ̲r ̲c̲l ̲e̲
a)
> > _ ×
Point
T
Boiling
b) CH3F < CH 3cL < CH -3138 < CH3 I
>
Increasing Motor Mass
Boiling
Point
Increasing
c) ctlzcl L CH 2C / 2
< CCI 3 <
CC /
y
P block C̲ i ̲r ̲c̲l ̲e̲
c) Lattice
Melting Point :
depends on
Packing
Experimental ( NCERT)
Refer
Most
symmetrical structure has
high M pt .
◦ -
P block C̲ i ̲r ̲c̲l ̲e̲
d) Dipole Moment ly =
q
✗ d)
tf 8 CH3C1 > CH 3 F > CH 3138 > CH3I
distance dominate
e)
Solubility
Alkyl Halides are soluble in non -
polar
solvent -
( Benzene CC /
u Toluene )
,
,
RX are less soluble in water
f) Bond
Energy
c- F 7 > C 7 C- I
c- CI -
Br
strongest
Bond .
P block C̲ i ̲r ̲c̲l ̲e̲
Chemical ( Reactions)
of Alkyl
Properties Halides
a) Nucleophilic substitution ( SN )
b) Elimination Reaction (E)
c) Action
of Heat
d) Wurtz Reaction
( Formation
e)
of compounds)
Reaction with Metal
organometallic
( C- Metal)
f) Reduction
Isomerization
g)
P block C̲ i ̲r ̲c̲l ̲e̲
Wurtz Reaction
☐
OY ether
2 Rx + Na > R -
R + 2Na✗
source of e-
CH3Cl 1- Na - CH } -
CH 3 + Intact
ÉH } ÉH3
NOTE : it is a Free Radical Path
:
symmetrical Alkanes are formed (R -
R )
8 Ease > RCI
of Ren RI RF
> RBR >
Q CH
}
-
CH -
I ctlz -
EH EH -
CH
}
'
l '
CH } Dry ether
CH } CH3
↓
P block C̲ i ̲r ̲c̲l ̲e̲
CH CH
CHZ
-
CH
-
}
-
I 1
CH3 CH3
b) CH3CH2Cl CH3 CHZ CHZ CH 3 1- 2 NaCl
- - -
together
\
.
I
CH3{ Hz [ H2 -
CHS
①
Nat
P block C̲ i ̲r ̲c̲l ̲e̲
In text 8 10 .
2 to 10.6
"
P block C̲ i ̲r ̲c̲l ̲e̲