Chemistry of Di-Halides & Tri-Halides

•
May eat fruits/chocolates %?
 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 PCl5 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:

✗ =cf
4 "' "
¥ -

officinal
¥
Aikens ( IFFI) dihalides)

CHz=CHz ; RCH=cHz j RzC=cHz ; PhcH=cHz

⇐ c-
HXCI.eu
-
E=€
✗ IF HX
Alkynes ✗ I ?
it
✗ M -
addn ( ?)
c- d-
( germinal
-

' '
n
dihalides
×
 CHECK
HCl
H - I __ c-u
HCl
H El _c%y
-

2.
oeq El 4 di
q ,

CHZCECH HCl
cuz -c=cy
hcl
(Terminal
T
in
position
2-
oea T ti f gl
,
gem

Ph HCl
M -

position
CECH
cnz-g-c.lt
-

,
2.
oeq Ph -

C=CH Cl

d, te non -
Terminal
HCl ( gem)
CI

Ph -
IC -

CH
}
di
 2. By Action of PCl5 on glycols & Carbonyl compounds:

Glycols :( vicinal diols

PC 's
ye
10h
-

of
104
Jg -

Cf + Pools
p/Brz Cl di + HCl
(vicinal)
•
Carbonyl compounds :

CI
PC /
d-
>
5
=o - + 10093
Pots £1
RCHO RCHCIZ gem
B- Pas
R-É-R
R
§
-

di
 "5
Ph -
CHO Phctlclz + Poclz
0
0015
'd + Poclz
CHJ
-

CH } cuz
-8,3-92
PCIS
+
CHZCHZCHO Et Chaz 3)

PUS
Ph -
CHZCHO Ph -

c4zC4Uz 1- 1)

Benzyl aldehyde
Ph -Ñ -

cuz
Pas
thief ,
+ s,

%
Acetophenone
Chemical Properties:
1. Action of aqueous KOH I
EHaq .

Vicinal :
°"

3- of
di di Hzo
£Haq→ } -
cf
104
Csn] ton
• Gem :
glycol
R-cn-ct-4aap-c.jo diols
"
gem are
-

CI -
terminal ) on unstable
CI 04
-
-

Hzo
R d R
a"

R d R
fan aldehyde)
- -

R
-

Cho
di du

R -
É -
R ( a ketone)
-

nzo
 OH -aa
• Phctlclz Ph CHO 1- H2O
benzol dichloride

Than

Phctlz.CHO-hzo-OHaq.ph
•
Phctlzchclz

É -
É -

cuz Ph -
-

cuz + H2O
di
2. Action of Zinc Dust :(usually for vicinal mainly)
2h

¥-4 ' dust

ot
> =
Cf + Znbvz
Br Br o -

Zn -
Br

an
¥ 5=4 + 2h Bvz
BID Can alkene)

AK
3. Action of alcoholic KOH / NaNHz or
1 .
- KOH

Br PBR
2 .
NaNHz
-0ha / c

n _¥- E- n
54THBU % µaNH2 )
/ -
H Br Bv
ak
]e=cM 2. oeq

µ ↳
cnzBr vicinal (vinyl bromide
)
p elimn
dnzBr
-
-

- anti - elim
 Br 9 -04 ale → can't abstract
vinylic H
'
c= EH
" Na+ÑH2 H
H UH ( strong ) → CECA
-

✓ Base -
HBV
an alkyne

µ§z¥
•
Gem : " "°

or
C- HBD →
Hzc=CHBr
ÑHZ vinyl bromide

HCECH THz
-

HBV

"3H6Clz( gem

nzcina ,
.

z.im,
ale -04
or ¥7
2.
Oeq
??
4. Action of alcoholic KCN
KCN-ECN-alc.co
vicinal :
Eton

CN
> c- et
ale
Je1 -
of
vicinal
Br Br cn
IN
(d) cyanide
Gem Br
• :
an 1 IN
d-
g
c-
- -
-

ate
LN
I

Br

Pr CN

d- CN

& d- c- d-
'

g-
-
- -

I an
1 I
BV
IN
IMPORTANT Reaction :
(For problem solving past )

Hydrolysis of cyanide
É
• s :

4351
" 20
RCN = R - -
OH
H -1

430-1
(Acidic hydrolysis (acid
Phew
Ph COOH
(Benzoic acid
-

trap : RX RCN 430-1 RCOOH

KCN
'

: Hzot
Note : RN :c RNHZ + HCOOH

(isocyanide) 1° amine (formic

acid
)
•
Action of heat on
dicarboxylic acids : -

COON °
*
doom
( Hzcz 4) H2O 1- CO + coz
T

(oxalic acid ) T
dehydration f decarboxy
-
cation
-

"
decarboxylation
°

* Enz coz + cyzcooy

-
COOH (Madonia acid) 0

* cñi°&? o
no +
CUT
dna ! '
kHz
cook !
¥
-

(succinic acid
(succinic anhydride)
 É -9% "

:
Eyck
* -

o
"2-

i
'
nzo +
o
' '
/
cuz
-8-0-7 -
.

cuz
§
-

glutamic acid
glutamic
:-O
. -
-

anhydride

i
'
* cuz cuz i
IF
-

i.
.
H2o + coat °

-492-9, ¥4
'
30k
Ccycwpentanone
.

Cadipic acid )
0

2£42 - E -04
* cut H2O 1-
coz 1-
0

\
cuz -

cuz -7, -
OH
( cyclohexane)
( Pine acid)
Note :
Czltcclz : Isomer -1 Ctlzcttcfz
Isomer -2 CHZCHZ
d' d'
C-Nak
•
Chzcttclz
•

↳
gin 430T cyzcy-
COOH

2 .
Hzot You
→
COOH
(gem) a- Methyl malaria
3. 0
acid

coz
-

,
IN ale CHZCHZCOOH
CHZCHZ H30→
Y2CN
•

di di
z .

µzo+ Cuzco 04
I
3. chin
•
cuz COOM
-

Ciccinal) "
2° Guccini acid
cuz coz
-

tyto / HW : ↳ Hgclz ( all

products
0 hzot car
-
vicinal
isomers
Eton gem
??
-

-
isolated
 Chemistry Of Tri-Halides (Haloforms only) : CH ✗
3

Preparation: (only Gem)

1. Haloform Reaction : (General Method of Preparations)
For Chloroform :
1. By Distillation of Ethyl Alcohol using Bleaching Powder
2. From Methylated sec. Alcohols & Methyl Ketones
3. From Carbon Tetra-chloride
4. From Chlorination of Methane

For Iodoform :
1. From Ethyl Alcohol
2. From Methylated sec. Alcohols & Methyl Ketones
Haloforms: cnxz
( ✗ f- F)
: Chaz
CH Brz
] Tan colour
( volatile
liquids
ch Iz ] yellow solid
General method :

cuz - I -
R
ketone
OH + Xz CH Xz
methyl
-

or

( ✗ =C1 ,
Br> I ) +

R R Coo Na
cuz
gun
-
-

2° alcohol
methylated +

(Nax +
tho
R= H
; Alkyl ; cyclo alkyl ; Phenyl
•
R -
É -

cuz + 4 NaOH 1- 3×2 CHXZ + 3 Nax -13420

@ethyl ketones Chalo form ) + RCOONA

94
•
R -
ch -

cuz + 6 NaOH 1- 4×2 CH Xz + JNAX

fnethylated
Halo
forms + 5420
2° alcohols + RCOONA
,
Visualisation of reaction !
I. oxidation
I.
Halogenation (d)
II. Nu -
addn - elimn = substitution
IV. Acid-base reaction
 I. oxidation : NaOH + Xz → N+aÑ×
-

Ex () + ✗

cHz-É
= = o

cuz _É^n -
R R
-

@ xidising)
2° alcohol Methyl ketone
methyl
fresco nance

II. d-
halogenation :
-( base)
stabilised )

• R -

g
-
✗
cuz
15
on
Enotisation R -

"
_%z
0
Flux To Go
(
-

acidic
]
now -

H2O
R
q=CHz
-

R c=C4z
^
-
-

OH '

10h
-

•
Base
catalysed
Enolisation
 R-qEÉnz
" ←
* ×
-

✓
•

R o
cnzx
Pon
- -

¥nÑ+
×
-

+
end ✗z U
R -
c -

CHZX R -
C -

CHZX
→ →
•

o
"
to
Cmono -
d-
halogenated
R -
c -

CHXZ
ketone
"
O
enof

✗z

R c. ✗
(2) halogenated
-
c -

3 Tri -

¥
•

Ketone
?⃝
 -4,555
-

ÉÉÉ×s
II. R H
R
Go Nu
-

Nu -

addn

(Tetrahedral Intermediate)
I 8+7
R -
c -
OH + c- ✗z Nw -
elimn .

IV. [ Nu -

addm + Nu -
elimn]
acid-base te
Nucleophilic substitution
ve
charge
- .

(SN)
CH Xz over carbon is stabilised

+
halo
form via back
bonding a
good
due
coat Nta
to 3- ✗ atoms leaving group
R -

↳ resonance
stabilised
• For chloroform ;

É-c-a@
0

R - I -0+3
NaOH
→ Is R -

a, ↳
OH
-

° Hzo
R - E _5Ña 1- Chaz @

For Bromoform
É
:
.
•

07 oxidn R
-

R Gt3 CH }
GH
-
-
- -

pg
OH

R -
É -

CBVZ

a
On
-

CHBR
,
+ Reootva
Base
 -
iodoform :

CD
-É-R
Riggins cuz
=_ →
I
,

I
Janis ← É Iz -
c- -

+
IR -co5N+a
•
Chloroform from bleaching Powder ?

Caoclz Ca( 0h12 + clz

c¥+o- a + a-

↳ ( O)
0dg
a- + :
 cts
C- H3CHz0H
CHz H
§
- -

(Ethyl alcohol)

93C -
É -

(chloral)
É Triclnloroacetadehyde
←
te
Cbc
- -
•

ca(0H)z
→ cuclz (e)
←
Industrial

Chloroform
= Chloroform +
(H-§-o)zCa
calcium formate
clzc % -4 AOH
%_oNa
-
•

→ →
clz Chaz + H -

Pure I
used for ←
form of chloroform
(medicinal purpose)
 importance of chloral :

Chaz cool , :
Cphosgene)
d
highly toxic .

• Chloral is transported cis t.be

form of
chloral hydrate ?? Hao
clz -
c-CHO → Clzc -
CHO . H2O
or -1
E- - - - - 40
due to chelation
C d- •

not
Cl
1 ( intramolecular
NO H
CI
g-
-
- - -
-

bonding
chloral is stable
•

Cbc -

Cholon) ¥
Chaz
 From Methane :

h°
Cltq + 3012 Chaz + 3 HCl

* From Cola : ( reduction

Coq + Fe
/ Hzo ④ 0493 + HCl

A)
 CHEMICAL PROPERTIES Of Chloroform & Iodoform
1. Oxidation ✓

2. Reduction ✓

3. Heating with Silver Powder ✓

4. Nitration ✓
5. Condensation with Acetone ✓

6. Reaction with Alkenes 6 39,10

,

7. Carbylamine Reaction are left

8. Alkaline Hydrolysis✓

9. Riemer Tiemann Reaction

Next class
10. With Na in Ethanol
Note : Iodoform Reaction & Iodoform Test 21/6 ( Moh)
3.30 PM
1. oxidation :

air
Chaz +
Yzoz COCK + HCl
eight
Phosgene
a- % -
CI → (carbonyl )
chloride

(highly poisonous gas)

Important : •
store Chaz in dark brown bottles
•
store is dark

fill the bottles the brim

•

upto
•
better to transport Clzc -

CHO

(chloral) & prepare on

spot
* best is to use 1% Ethyl alcohol
Role
of Eton when added to chloroform :

EtoFÉÉ -
c,
" Nu -
add "
Eto -
É
elim
U Nu
?
2. -

+ HCl

Diethyl Et -0 -
c -

O Et Eton
carbonate ya ,

= Non -
Toxic
Eton
↳ diethyl ester
HzC03
of carbonic acid

Note : 4 CHI 1- 302 400 1- 6Iz -12420

}
2- Reduction :

Zn / HCl
czyzclz + HCl
Chaz
Zn / H2O (9)
csyzcl -124C /
an / HCl
C Hq +34cL .

Excess]

silver
3. with powder ( heating :

zcnctz-61-g-HC-CH-61-gcln-o.EE/--------e,;. -ci-6Ag-a=c -4

n e- c- H
a
I
-

=
1- - -
-

Acetylene
-
- -
 G

§
-
⑨
R -
c
-
c ,
+
GAG 1- c- R É
di ,
R -
C C- R
R=CHz
+

6
Ago
② Phcdz +
Ag % Ph -
C c- Pb

Benzo -
chloride diphenyl acetylene
( Tri)
(O)

Na0Hage@cessj2PhcO0H2.H
1.

(hydrolysis)
 8 . Alkaline hydrolysis :

gem
• -

µ - ga -
Haa
H -

Trio /

d,
a
CSN] iii. ( unstable
-
H2O
°

É
-

n
n E -5kt n on
Chaz
-
- -

(NÉ) 4
chBrz Koltaq or Nao Haq
Ht
CHI] alkaline ( Base)
acidification
•
KOH H -
É -
OH
formic acid
2.
Ht
 N°0 "
Rcxz RCOOH
2. Ht
1. NaOH
Phc ✗
z
Ph COOH
-

z .
µ,

•
hydrolysis of gem
-
tri halides
 4. Nitration :( HNOZ conc
)

aFc÷ñIñn=°
CI

Clzc -

Noz
'
- - - - -
-1 →o
Cl
.

(Chloropicrin)
•
insects .de

5. with Acetone . used in chemical

:
ware
fare
↳
•

highly poisonous
CHA a-

% -1=8 -
2 . ↳ + CHz\ /
OH (E)
cuz U T
,

Et ↳ t.NU

(Nucleophilic Addn)
( Nu addn
-

product)
 4
•
Clzc
-
H
93 + Hzo
ale
( 1,1 -

Elimination
✗ - elimn

Ctzc : a Nw

St
CH3
-4=0
↳
Icts cnzz.sc
}
NU
↳
-

CHZ

OH H
CHI -
-
CMJ Caz
Chloretone : • a
hypnotic drug ( used in
sleep
• colour
crystalline cisducing medicine
solid
 r

Chloroform | Memory Map

Reactions

HC(OEt)3 Na O2 COCl2
(Ortho formate) CH3CH2OH h! (Phosgene)
EtOH
OH (Et)2CO3
CHO OH
H+ [H]
CH4
NaOH, " Reduction
o-Salicylaldehyde Reimer-Tiemann
CH2Cl2
Reaction

PhNH2 Ag
PhNC HC % CH
Carbylamine KOHalc., " "

CHCl3 HNO3(conc.) Cl3C # NO2

(Chloropicrin)
Chloroform

RNH2 (1$) (CH3)2CO OH

RNC
Carbylamine KOHalc., " KOH (CH3)2 - C - CCl3
Chloretone

RCH # CH2
RCH = CH2 1. KOH(aq)
C HCOOH
KOH 2. H+
Cl Cl

Note : The reactions of Iodoform are almost similar to that of Chloroform except the following :
CHI3 + O2 CO + I2 + H2O
CHI3 + AgNO3 AgI& (Yellow)
CHI3 does not give Reimer-Tiemann reaction.

Note : Haloform reaction :

OH O
CH3 # CH # R CH3 # C # R + NaOH + X2 CHX3 + RCOONa
(X ' F) Haloform
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓