Chemistry of Di-Halides

Germinal @ em
) Halides :
Atkylidene Halides
Terminal Type : Cltzclz ; Cltzcssclz ; Cltzcltzcltclz etc .. .

"
cñ
If -

\
, ,
Benzylidene chloride
(Benzol chloride)
Non - Terminal ( Internat) :

Cl
T'
d Hzc
-

CHZ -
C -

CH
]
Cltz -
-

Cltz
1
C1
di
(sopropylidene chloride) (Sec butylidene
-
chloride)
 Vicinal Halides :
Alkylene Halides :
I
> ? I
'

c -
c ✗ atoms
-
on

£
'
atoms
adjacent
carbon
×

cHzCH2 chloride
°

di El
:
Ethylene

• CH } CH -412 :
Propylene chloride
di El

E- E- it
•

{
E- E- E- i
di di
&

di Li
}
'
Pe 33-Type_
 Chemistry Of Di-Halides

Preparation:
1. From Alkenes & Alkynes:
2. By Action of PCl 5 on glycols & Carbonyl compounds:

Chemical Properties:
1. Action of aqueous KOH
2. Action of Zinc Dust
3. Action of alcoholic KOH
4. Action of alcoholic KCN
Preparation:
1. From Alkenes & Alkynes:
✗
vicarial dihalid.es
1 .

C C
Cela,
C C
obs : É' ✗ atoms
£
.

added to
(Anti)
are
✗ ≠F
side
opposite
✗ 4- I f.)
vicinal di iodides are unstable
(anti addn)
-

CHz=CHz ; RCH -_CHz J RzC=CHz j PhcH=CHz

-
c=c -
"×

1.
-

c=c
/
-
HX
¥É
Oeq \× / '
µ 1. oeq H ×

(vinyl halide ) M -

adds

gem-dihah.de
 •
H-CE.CM
HCl not -
cñ
"

Ethylidene chloride

'
"
2.
oeq h -
, ,

AM

t, C'

HCl
na fl
•
Cuz CECH cuz 'c=cH Cag
-
c-
cuz
'
↑ 1. oeq ↑ n 1.
oeq &,
M (Maddin)
pq Non - Terminal
(Gemina)
91
Ph HCl
CECH Ph c-
cuz Geminayintevwal
- -

di
Phenyl acetylene
2.
oeq
1-9

HCl
i' ↑
CH3c=_ c-
cuz CUzC= c-
Cng cuz
-
c- c- cuz
2.
oeq d, '
n di h

Germinal internal
2. By Action of PCl5 on glycols & Carbonyl compounds:
•
Glycols ( vicinal diols
) :

PUS + HCl
\ I of 1- Poclz
{
.

C- c.
/ / I 1
I
on by Cl Cl

( vicinal)
P/BV2
¥ -
ch + 43100=3
A

br br
• Carbonyl compounds :
C1

=o + Pas
d- ( germinal )
pas
del t Poclz
HCHO Ctlzclz
Pas rhinal
RCHO Rcuclz
'
Pas
R R
q Ricci
-

internal
-

' ,
◦
R
 "5
Ph
PhC4CfziBenzal@i1chlorideCBen-zyli.d
-
CHO

] .ene

◦
>
Cls 7
'd cuz
CHJ CH } C CH
lsopnpytidene
- -

]
-

£,
chloride

PCIS
CHzCHzCH0 cuz
-

cuz
-

e-nclzn-p-ropyh.de ne
chloride

Das
Ph -
CHZCHO Ph -

cuz Chaz
-

Terminal
gem

V5 91 Non -

Terminal
Ph -

cuz Ph -
e -

ens
di
Chemical Properties:
1. Action of aqueous KOH = OÑaq ( KOH
/ Hzo or NaOH
/ 420)
• vicinal dihalides :

-0499
\
f- of → f- of
' '
vicinal diols

di di (SN) on on

Germinal dihalides :
-

ion
•
_

'

-04 t i
É ¥
diols Unstable
'
"

¥ gem
:
-

-
-
c- .

-
a ¥É :
- d -0=0
hydrolysis of di halides
-

-420 I
•
a carbonyl
group
 OH -aq 04
• PHCHCIZ Ph -

Caton -420
> Ph -

4=-0

Benzol dichloride Unstable

Benzaldehyde
ÑHA "
PHCHZCHO Benzyl carb
aldehyde
•
Phcnlzchclz

91
THaqph-g-cuzAcetophenone.ph
-

C
-
CH }

di

•
Chzctlzcuclz
ÑHa9 CY > CUZCHO propanol

CI
-OHaq § Propanone
& -043 cuz cuz
-
-

Cuz
-
.

CI
( acetone
2. Action of Zinc Dust ( only for vicinal halides
St E-

Zn - Br
n

Jc d-
:&
-

anse =
' '
-1
Br Br
?
Br
+

2nBvz

AK
3. Action of alcoholic KOH / NaNHz or
1 .
- KOH
2 .
NANHZ
H %) n

n
# {
Br on
_
or Nantz ( 2. Oeq )
his
Hint
4
ale = c-
'
dibromide HBV Bv
Ethylene -

(vinyl bromide)
 HIE -4 ÑaÑHz 1=1 -
c -⇐e -

y
NaN'm
cuz cuz
-

, >
H
/P ✗ '
Bv
alkyne
'
¥32
strong Br
an 2.
↳ base oeq
(vinyl bromide) -
HB,
* a Hz
alc KOH
Cannot abstract NaNHz
2-oe-qcngcniI.3.kz .

vinylic H -
atom
1. Oeq

alc
•
{ Uz -
Ey -

Br
Kon C9z= ch -
Br
P I

Br -

ltBr vinyl bromide

C. ◦
eat

yourself ale -04

¥2
.

CzH6C1z(9em&
vicinal )
or
??
2.
ÑHZ 2.
Oeq
4. Action of alcoholic KCN
KCN-ECN-alc.co
vicinal :
Eton

CN

CI
'

/
c- oh > -

, I 91C
/ 1 I
Br Br CN di
Sa, CN -

cyanide
(vicarial)
Gem "
◦ :

it CN
-

T
CI >
d c di
cyanide
- -

c-
-
- -

91C
1 / I
SN CN vicinal .
IMPORTANT Reaction :
(For problem solving part ]

Hydrolysis of cyanide :

0 +.

H -30-1 +
11 V44
RCN > R -
C -
04

◦ (a carboxylic acid )
↳ ◦+
PHCN Ph - É -04 (benzoic acid)

Note : ak Not
Rx RCN Rcoon

up ↑
Kay
( R -1-3 ) No SN Rxn in → step .

; R≠ph ? aryl halide

Hydrolysis of Isocyanide s :

430-1
RN :c RN Hz 1- HCOOH

1° amine (formic acid)

cleavage
•
Action of heat on
dicarboxylic acids

COOH 0
*
doom
( Hzcz 4) H2O + co + coz
dehydration decarboxylation
(oxalic acid ) decarboxylation

✗ COOH
* CHI coz 1- CUSCO 04 tnonocarboxylic acid
-

Coz
-
COOH
(Mahonia acid)

É oiiii
2
'
cuz cuz
-
- -

* l
I 4 ,
5
i o =

cuz her cuz

cg
"" a
- -
"

3 -
-
- 11
0
succinic
anhydride
(succinic acid
 É_
2

* cuz -
☐ iii. :

CHI
*
"
'
3 '

, i
Glutaric
'
4
cuz
-

É -1%,
.
'

anhydride
0

glutamic acid
"
"

3 z
i i.
,

*
GHz cuz
-

4
Cuz
i.

E
1 "
cyclopentane one

Cuz -0-7
-
- - '

5 11
. -

420
coz
-

adipic acid '

' '

y
3 2

÷?
" " :

* iñi = .
.

" cyclohexane one

\
cuz cuz -9, -1,0-4
'
-

J 6
0

Pi melic acid
 Action of heat on Pthalic acids ( Cs Ho 04) : O
, P, M

%
coÉñi C
'

' ;
i ,

Cooke
§ Pthalic
'

.
-

Uzo
Pthalic acid
0
anhydride
-

COOH

Nothing happens !
COOH

m -

Isopthalic acid

COOH

Nothing happens !
COO H

p
-
Tevpthalic
acid
 Q.cz/t4C1zlsomer-I:CHzCHCfz;Isomer-1I:CHz-chz
1 di di
gem
vicinal
1. Kcal
•
Chzcttclz 2.430-1
(gem) " • °"

kens Acn
.

✗
nzot /
cuz CY
-

,
alc \
ICN COOH D
( gem ; dicyanide) ✗ -

Methyl
tnalonicacid -
coz
CHZCHZ 1 KCN cuz
•
-

cuz
{I cuz CHZCOOH
.

£1
-

I 1
2.430-1 CN CN 430-1
(
vicinal) 3 . A

succinic acid
cuz -

cuz
{ 004 { 004
-
H2O
Try Yourself : C3H6Clz ( all isomers is
eluding Gem, vicinal &
isolated)

1. Kavala
↳ HGCIZ
.

2.
430-1
3.
4. we .

CI
0

Cl
Cl

•
Cl

Cl Cl

:
Cl Cl

(isolated )
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓