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Haloalkanes and Haloarenes Shobhit Nirwan

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NAME REACTIONS OF THIS CHAPTER
4) FinkelsteinReactio
+ Na
R X
-
(this
Acc
(2)
-
I
to
-
I
+
[✗
Nax
direction
be
can
R
-
favoured in forward
Le chattier 's Principle]
reaction
.
preparation)
(Alkyl halide
by precipitating
]
Nax with
dry
acetone
.
Swartz Reaction :
R
-
( ✗ Cl
=
,
✗
+
Hgzfz
( AgfSbfz
,
salt in
→
,
Swartz Rxh
(3) SandMayer 's Reaction :
Cl , Brand CN
florid e
Metallic
Br )
Finkelstein and
Halogen
[v11) ion
presence of
exchange
in the benzene
ÉÉ
+
chloride
+
CUCNIKCN
↑
K3B= :
Diazotization Reaction :( How
Diazonium
dilute
Gotts Need)
is
HCl with ag Solh
.
formed )
cold solution of Aniline in
HNOZ / HCl
ey:-(Hz
Ig
:
-
-
( Hz
2C Hz
-
-
2N a
Br
✗
+
+
2
(0-52)
Na
.
dizonium
chloride
Benzene
+
Nat Bo
2
excess
Nice
or
ts
Wurtz Reaction :
X +
N2
this Benzene diazonium chloride Ps
Aniline
-
benzene diazonium
Ne
prepared by treating ice
of NaN02 at low temperature
4h2
R
ring of
.
Na
+
ÉÉ
"
:-)
"
ox
.
Benzene diazonium
*÷:
Agx
+
-
)
easily introduced
be
can
R F
-
Cofz ,
Nice
141
Cl , Bo
=
-
X
-
[ Hz
-
R
Ctb
ᵈ%
¥É
R
-
Ñ
(H }
-
Ctb
+
R
+
( Hz
-
ZNAX
cuz
2 Na ✗
-
Ctlz
-
CH } -12 Na Bo
g
(5) FPHPG 's Reaction :
2
(6)
wuotz
-
fitting 's
+
(7) Reaction
+
CH }
-
+2 Nat
( Grignard
R
-
✗
My
+
&¥
2Na+R-✗
ie
Cd
with metal
&¥
reagent )
R
-
1
:
++AñA→
,,
lit
-
mg
lfñedel crafts
rule
CH3-CY-CHz-C.tk
-
-
( Hz
-
-
.
.
.
✗
Grignard reagent)
my
+
µ
+
(minor
'
r
Acylation]
(mpno , ,
alkene is
major)
-
r
(
major)
cl
KOH
1-
.
CHE CH
( Hz
-
CH
-
.
(
☒
+
Auto Phenom
major product
-
Note : Now we'll use these Name reactions
of the reaction
É
products
ie
Br
name
%
R
/ B- elimination / dehydro halogenation)
B
9
B
:
Alkylation]
alkyl group containing
Rule : More
G-
-
-1+r-etA
(9) Saytzaff Rule :( zaitsev
Nacl
Cd
[Friedel rafts
2Na✗
:
i
(8) Friedel-Crafts Reactions
+
+ 2.
rÉmjÉr
↑
2Na✗
Reaction :
+
egfo
zµa→%
further
-
=
CH 2- ( Hz
CH
-
-
C Hz
Ctb
-
CH}
lmajorproduc.tl:2
alkyl group
in these notes
by mentioning only
PREPARATIONS
HALO ALKANES ?
\
(1)
\
\
\
\
\
from Alcohols
→
Luca's test
( Luca's
reagent
R
OH
-
→
R OH
.
Anny Znllz)
.
R
-
502 and HCl
as
socdz
+
-
cone Hilt
Hcd
+
( best process
Darren 's test
=
is
Ll
released
as
gas)
+502-1 till
R Cd
→
H2O
+
-
Tnionyichloride
→
R OH
→
3R OH
+
-
-
Nabs
Hzsoy
+
PX }
+
R Bo
→
3
-
R
-
Natlsoy
+
-
H2O
1-
X 1- H3P0 }
/ Boric acid]
→
R
-
OH
É
R
-
✗
✗2=882,12
→
(2)
R
-
OH
Pcls
-
Poclzt
+
HCl
:
From Alkanes :
%
RH
%)
CHICHI
two
type
from
R
✗2
+
product
→
R Cl
-
Hydrocarbons
from
→
+
-
of
Cha
H
,
-
+
HX
( d- CH z
( Hz
there with Cl
-
CH z
C
-
Hz
-
CH}
1-
( Hz
-
CH
Cl
-
[ H2
-
Ctb
on
diff position
.
.
Alkenes :
Hydrogen
Halide :(only
> c=c(
( Hz
elf !
-
Add
"
of
"
-
Halogens
H
add "
of
/
/
\
+
Brill
_
HCl
,
1)
>
c-
CC
'
H
×
CH }
-
-
CH
-
( H2
de
it
:
H
c=c
Bo
tix
+
( H=CHz
-
131 from
✗
so 2
will be
"
f) Add Of
E)
-
+
Boz
→
Boz
-
CH,
-
CHZ
-
Bo
H
Pnccdy
to
alkene give reddish
boom
fumes help
Halogen Exchange :
By Finkelstein and Swartz reaction
(mentioned earliest
in detach of =/ bonds
-
.
HALOARENES
\
(1)
from hydrocarbons
☒
(2) From amines
by
\
by electrophilic
""
sand
*
\
\
I
substitution :
Feo
×,
\
'
✗
+
dark
-
£
halo toluene
p halo toluene
:
Meyer 's Reaction
-
NÉX
_
☒
NHZ
-H✗
273 -278k
Benzene
diazonium
halide
Ni"
( ✗ =ce,Br)
×
+
Aryl
Iii
If Iodine
[
,
then
no
Nik
Nz
Halide
cuoeguired :
-
#
[
+
Nz
CHEMICAL REACTIONS
HALO ALKANES ?
Nucleophilic
-
→
-
nu
+
substitution
=,ÉÉ
\
→ Ni
¥
-
nu
-
✗
+
-
other gins in table 10-4 but main I
É RCN (Nitriles
,
R
-
✗
/A
SN
-1¥
R ONO
-
RI
sp2
Rz
N0z(Nitro alkene )
-
attack fromsides R
,
Rig #
s
R2
R
/ Alkyl nitrite)
mechanism :
reaction
'
( Pso nitrite)
RCN
1¥02
→
\
\
\
"
R
both
/
!
NU
f-
mechanism :
SNZ reaction
↑
/
փ
c- ✗
HI
i > 2° > 3°
(2)
no
c-
-
-
-
R
-
)
×
/
µ
-
ni
-
/
NV
352° > I
mixture)
( Racemic
↑
-
+
Rs
R,
(carbocation)
→
%
,
↑
/
µ
Walden
Transition state
inversion
Elimination Reaction:
↑
-
'
B
B-
I
c-
/
g-
-
¥C(
,
✗
=
leaving
e-f-IHzc-CHz-ctl-CH-CH3-tlzc-C.tk
-
→
H
+
×
group
in
Ctb
-
metals
with
Grignard
Wurtz
:
Reagent
Reaction
/
]
both mentioned
earlier
CH
-
CH ,
↓
( 81% )
→
-
×
B- Base
(3) Reaction
B
+
Hzc
-
Ctb
-
Cha
-
CHE CH
( 19%1
HALO ARE NES
\
(d) Nucleophilic
-
4
it is
And ,
affordable
if
we
very costly
Ps
add
more No,
more
N°2
;
→
ÉN°2Na÷¥
N°2
↑
alternatively
temp
→
,
NO2
¥-0m
-
ce .
Nitration :
Ran :
Hoa
Call
'
'
Para
products
ÉI
¥¥s
¥ÉÉI
Sul phonation :
③
Reaction
→
-
crafts Rxn
with
Wurtz
Fitting
ÉI
'
.
4¥
""
+
N°2
+
( mentioned earlier)
metals :
fiHPg
major)
sH ÉI
!
friedel
→
te
ie
→
IN Oz)
easily
am
N°2
No
ce
el
↓ and
N°2
→
+
add
↓ 02
Electrophilic Substitution
Halogenation :
ÉÉ
we
402
↓oz
12 ]
so
ÉT
Hoz
add
,
gaps
N°2
:
%
at ten
so
.
Éy
.
Noz
I
( Dow's Process)
Phenol
Cl
add more
\
¥;¥"Em
[ This process
ie
\
\
substitution :
Chlorobenzene
→
\
'
/ mentioned
earlier)
£03M
"
occurs
.
temp
PHYSICAL
%
%)
They
are
colourless
Polar but insoluble in creates
%) Soluble in org
F) Polarity
]
✓]
vis
PROPERTIES
Boiling
point
melting Point
solvents
.
R
-
✗
> R
f
<
•
Cd > R Br
Molecular wt
( seen
II.
-
> R
-
-
2.
by symmetry)
<
-
I
R f < R ce CR Br CR
-
-
¥
[
de
-
-
I
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