Preparations-II -

I
 Organic Halides
Preparation:

1. Halogenation: 2. From Alcohols:

(A) From Alkanes (A) By Action of Halogen Acids
(B) From Alkenes (B) By Action of Phosphorus Halides
(C) Allylic Halogenation (C) By Action of Thionyl Chloride

3. Halogen Exchange Reaction:

_

4. Hunsdiecker Reaction:
(A) Swarts Reaction
(B) Finkelstein Reaction
2. From Alcohols:
(A) By Action of Halogen Acids ( HX ; ✗ =/ F)

zone + ¥5 -

R X -
+ H2O

an alkyl halide

Substrate
Reagent Product leaving group
* The
given reaction is
referred to as :
Nucleophilic ( SN)
substitution
of 1.1 ( halide ) ?
-

IP : Role HX not ✗ ion

.
Why use

Ron + -04 !! this reaction is

-

× 2x + IMP
( KX )
NOT feasible ?
Note :
key factor in SN is role of leaving group - -
* A SN reaction proceeds spontaneously only if t.be

leaving is stabilised . Criteria is ? A weak base is

good leaving group ; whereas a

strong base is a

poor leaving group .

ROH + -04
-

In × 2x +
* the reaction :
( Kx )
OH is strong base hence the above SN
group a
-

reaction is not possible .

Hence
9+-1×8
* : -

zone + R X -
1- H2O
is a

spontaneous since the leaving group , H2O is a weak

base (a good leaving group)

Note : Ease of Reaction : HI > HBr 7> HCl HF
strong weak poor
Note : This method
RF & Rct
is not good for
Visualisation of Reaction : HX @
as I Hxcono
204 + Hxaa > ?
or
HX
F
conc
St

•
ROH t H -
✗
aq
2- f- µ + ×
-

It
( oxocation) : Not stable ?

• R£§ -
n Hzo + Rt :
Alkyl carbocation

Rt R X
-

+ X
alkyl halide
-

•
an .

↳ key point :
stability of alkyl carbocation

3%-1 > 2%-1 192 ÉHZ

Ease Rxn :( Wint ) 1°
of ROH
3920m > Upon >
:

ROM
( w.at
product :

z°R× > 292×7 PRX

Note : RCI is not formed ?
HCl is weak acid 273° RBV & RI are
formed .
* ROH > RX 1- 420
+
Hxcg,
How to HX ?
prepare gaseous

HBV HI

[ Not a good method

• NaBr + 42504 aHS04
For RCI ]
conc

(or KBR)
B. P
• high 1- HBr@D.lowB.P
. low volatile .

highly volatile
Ron NaBr R Br + NAH 504 t H2O
42504
, ( 1° only)
Note : As the reaction is carried out at higher
temp ; 293° alcohol undergo dehydration
alkenes 1° RBr
to
give only
( Not 2013° RBR )
 NAI 1- 431004 > Naz Poot + HI
•
(g)
Cor KI) low B. P
.
high B. P -

• low volatile .
highly volatile
NAI
ROH > RI t Naz Poy + H2O
HzP04 1° ?
* 2013° alcohols at high temp .
give alkenes

Hence the above reaction gives only 1° RI .

Note :
why can't we use Hzsoot with NAI or KI ?
42504 + KI → Kz 504 1- HI

Iz
Hzsoq oxidising acid
:
.

43 poof is not strongly oxidising ( safe method

 Znclz
* Ron + HCI RCI 1- Znclz 1- Hzo
(conc) anhydrous
Lewis acid 19293° ??
H

R§É -
@°I -

H 1- Znclz 2- +
-
unstable
znclz
•
an

( stronger bond ) § intermediate

( weaker)
-

Rt +
[zn( )Ck]
on
←
•
Rt RCI
alkyl ↳
Feet carbocation
good leaving
[ n(on)Uz ]
-

group
Znclz 1- 420

trap : since stability of Rt is the

key factor ; hence

1° Rct are not formed or reaction works for

2° Rct & 3° RCI only .
Lucas Test (Distinction between 1, 2, 3 Alcohols)
0 0 0

HCl
conofZnClz@nhyJiLucasReagentCL.R)
Znclz
ROH 1- HCI RCI 1- Hzo
conc
Cahhy)
alkyl chloride

Observation : If the solution of RCI in H2O turns

milky ( whitish white

or
give a
turbidity
Instantly ; then it means ROH is 3° .

. Roy
L - R
Rt : 3° most stable ; hence

formed quickly
soluble
• While turbidity ? RCI is less in 420 ; so they
simply float over Hzo surface giving
a milkiness ( while turbidity
or while fumes
Observation : If while fumes appear after a
gap of
3- 5 minutes ^
then it means alcohol
,

is 2° .
( why ? )

Irt is
fairly stable & thus it takes
time
for complete formation .

Observation :

If there is NO White fumes ; then it

is 1° alcohol . In this case
,
while fumes
appear on
heating ?
on
heating formation
. . . . .
of even

1° Ct is possible .
2. From Alcohols:
(B) By Action of Phosphorus Halides ( only for 1° RCI
)

+
* Ron Pas 2cL 1- Poclz 1- HCl

( PB.rs/PI-s) (1) Phosphorous

do not exist oxychloride

Ease of Rxn : Cuza > Ipsa > 20pct 30pct

* ROH + PXZ RX + Hzpoq

4 (E)
P/ Xz
• ( insilñprepn)
✗ : Cl Br, I
,

• order of Rxn : L°R✗ > 2°R✗ 3°R×

2. From Alcohols:
(C) By Action of Thionyl Chloride ( Darzen Reaction )

ROH t RCI + soz + H C- I

sock (9)
(g)
1° 3°
• ease
of Rxn :
Ron
> 2°Roy Roy

: 1° Rc , > IRC , 3° RCI

Note : Pure
form of 2° RCI is formed ?
502cg, & HCl
(g) escape
Note: We can also use to give Pure RCI .

solvent
Pyridine as :

Py CSHSÑHCI
-

RCI + +
ROH +
sock t, soz.gg, ( pyridinivm
(545^1) . ,- 1 .
chloride
 3. Halogen Exchange Reaction:
(A) Swarts Reaction ( only fluorides are
formed)

RX + Metal fluorides > RF + Metal

+ halide
Br, I
✗ =
C) ( )
-

F ion

RX -1 MF RF 1- MX

select method
Agx I
any
:
Agf
1,
Hgzfz Hgzxz
Cofz Co I
Xz
Sbfz Sb Xs I

:# Metal halides are insoluble

( precipitated Reaction will .

proceed in

Forward direction
Illustration :

1. HBr/ Peroxide -
F

IAgF
1- Butene
r
2.
Agf ¥
1.
NBSYCCKI F
→
2.
Agf
3. Halogen Exchange Reaction:
(B) Finkelstein Reaction ( only for Iodides )
Acetone
RX + NAI RI t NaCl I
MeC0Me
✗ Br ( KI)
or Na 'Brt,
= Cl
,
or
( Mezo)

it
'

* Solvent : Protic : is attached to most electro -

re
8-1 8-1 8-1 St
atom H2O ROH RCOOH ;
: ; ; NHZ
Aprotic : it '
is NOT attached to most electro -

negative atom 1.1 .

or -1
8-0 DMSO
Chez cnz ;
§,+
-
c -

St ;
too cuz cuz
- -

05 -
•
Dimethyl
THF Sulfohoxide
* NAI / KI : have strong covalent character ( weakly ionic
soluble in solvents
are
highly aprotic such

Acetone ( Free)
-

as = I

/ NaBv ionic but insoluble

* NaCl : are
strongly are

CKCYKBV) in
aprotic solvents resulting in their

precipitation forcing the reaction

direction
in
forward .

Ra lai
RI + NaCl
• ti are
precipitated
RBV Acetone Napa )
(
(Driving of reaction in Forward direction )
•
Ease of Rxn : BRI > 2°
RI
3° RX
Illustration : Convert propene → allyl iodide

NAI
1 .
NBS /Cela z .

I
→ acetone
3N

Identify the
products -
. .

3K ale HBV NAI

A D
-

B c.
O
KOH Peroxide Acetone
Br
* Brzlo : selective
(c)
(A) (B)
BV

Br

①ninor) (D)
4. Hunsdiecker Reaction: ( mainly bromides
)
.
From silver salts of carboxylic acids

R -
É -
o -

Ag + Bra
ccl4
R Br
-

+ coz (g) 1-
AgBr
60°C
alkyl bromide

% yield : 1°RBr > 2°RBr 3°RBr

: R Br > RCI > RI

t, I t
best poor
Not
formed .

Note :
§ -
o -

Ag + Brz
cat
Br + coz
60°C

(silver benzoate)
+
AgBr
(Bromo benzene)
Visualisation : (Free Radical Path)

0 0
a ~
•
R - E -
o -

Ag + Br -
Br R -
d -

B? 1- Ag Br
60°C

ep -

ep repulsion
is the cause

0 Bit R-É -0° ofhomolytic

É=o breaking
bond
•
RT 'd # + R°

Carboxylate FR CO2
(g)

• R° + Br° R -
Br
(alkyl bromide
13×2
Cuzco on CUZCOOAG CUzBr + coz + AgBr
⇐
l4, #
t,
-

Uzo y,

@ c- atoms) 1C atom
-

contd
(step
. .
.

down )
 Na° " Na 4
Hq
c-H-j-zgc.ae
Na C.
cuz Coon > Cuzco -0
> .

-0 ⇐
,
-

1. Ago -4
Ch :3 Br
2.BR/cc94
A

Note :
Why RI can't be formed .

is back
* R° + I° RI Iz given
too
large in
-
Coz
Csize)
what will happen ?

¥ '
R -0° + R° 3- c-o R
§
- -

I
Can ester is formed)
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓