Reactions of Chloroform

&
Chemistry of Grignard Reagent-I

( Do deep breathing)

•
May eat fruits/chocolates %?
 CHEMICAL PROPERTIES Of Chloroform & Iodoform
1. Oxidation
2. Reduction
3. Heating with Silver Powder
4. Nitration
5. Condensation with Acetone
6. Reaction with Alkenes *
special Reactions

7. Carbylamine Reaction of chloroform

8. Alkaline Hydrolysis
9. Riemer Tiemann Reaction
10. With Na in Ethanol
Note : Iodoform Reaction & Iodoform Test
6. Reaction with Alkenes

RCH =
cuz 1- CHAZ + KO
Hale ?
go,

€54
CI

•
a -

& -

H ( base] Ects
↳ acidic (? ) Hao
-

Cl

3- Cl
groups -= effect -
vet 8 cclzt CT
←
CEWG) Cdichlaocarbene
•
icclz : Free-radical (✗ -

/ 1,1
elimn -

)
elimn

( as electrophile)
→
RCH=cHz + Bcuz RÉH -

CHZ

nucleophilic
substrate
①
Kaz
( intermediate)
 RCH É8Cdz RÉH -

Chez

nucleophilic ( ① Kaz
substrate
intramolecular
attack
•
CHZ =
GHz I,
closure
•
CHzCH=CHz ring
• Ph CH =
cuz R -

CH -
CUZ

CI
¥
7. Carbylamine Reaction ( Test of 1° aliphatic & aromatic

amines
RNHZ + CHOI
]
-131<0
Halo RN °

° go -6oz
@ aliphatic) Isocyanide
( Carbylamine)
t,
unpleasant smell

1- zkcl 1- 3420

PhNHz + Chaz 1- 3 KOH PHNC

ale
(1° aromatic) Phenyl isocyanide
aniline ( Phenyl carbylamine)
Note : 243° amines do not give -13kV 1- 3420
carbylamine Test .
•
Cb - c-
Ñ HIk -
µ,
Ects
e,
-
: CO2

%? .in?-Icci- R-Ñ⑦_d
CI
-0

I
Cepdonav) Cfp -

acceptor) Lg Cl
lewis base Lewis acid

(Nucleophile) ( Electrophile) -04 ale

( base)
Elimn ?
2- Ñ=E C- 244)

(Ph) 2- N→=C (alkyl Isocyanide)

?⃝
 9. Riemer Tiemann Reaction : substrate : Phenol 0,4
*
Reagent :
Eocclz
Reaction :

04 04 04
60°C Ht CHO
Chaz
-
* + -1 NaOH
1-
(coho)
Eno
04 04 -0 '
'

(1) NaOH
ps
*
- cuz - Chi Csalicy / aldehyde)
( Il) Chaz
of o/p
' '
mix
0 - Cressy 60°C Eno P •
.

Ciii)
'

Ht
'

04
04
. ortho is
major
* "
- ago ( ?)

Stolz
1
Note : Rxn is
no ,

'p cresol £43

'
-
(1) 040-1 0
-

-04
: Phenoxide ion

Coase) ( conjugate base

)
(phenol :
acidic
substrate ( nucleophilic)
NaOH/ KOH
Phenoxide ion has

Gory
•

①
a
very highly
& activated
ring
soon . . - -
.

cii ) Cbc - Hottie -

Ic /
3
o
8 Cclz
-

hzo -
c,
-

↳
Electrophile
(reagent
 -

o -

o
"
-
Chaz
+ 8 Caz -

g. µ

-
(Nu)
o
-

o
- CHCOH)z
Ht -
CHO

-1120 diol
Ciii ) gem
-

( unstable)
OH

-
CHO

@ -

salicy / aldehyde)
 salicylate hyde ?
' '

Why o is
Major
4-
=
.

g-

•
observe intra -

molecular
C
*
-
H H -

bonding ( chelation)

(Extra stable)

'

°
=

* . + an
effect due to -
ve

charge over 0 -
atom

effect of ( only at
-

• + I 0
ortho)
I
5 is most strongly activating &
specially at ortho postion .
10. With Na in Ethanol ( Eton/Na = Eton

Chaz + Eton / Na .

• Eton + Na
=toN+a + Yz Hz T

1 ( Test of
Cl
-
alcohol sj
Eto÷¥
as Nu

É
-
c ,
1 U
Eto
-

as Nu -

CI
-

Ci
-

Gdi
OET
Eto
-

d Eto
-

Eto - -

bet riester
•

Ethyl ortho format

Iodoform Reaction & Iodoform Test :

"
"
an
org .

compd responds +
rely to
iodoform Test

YIz
a
CH Iz 1- Z

an
organic compd (4)
yellow Ppt
✗ must have either

of :
OR group
cuz CH cuz g-
-
-
-

GH it
o in
! !!
✗ :

cuz ch -
or CH
-5,9
-

?
-

In 0
 cn5§
cuz
-

ch -
or
?
-

'
on
? ?
analyse the side
product (2)
Nam
CH
sod .
salt of
RC Xz +
,H-CHz Carboxylic acid
on
✗z

→ Na
RCOONA
-

or

(-8+43) Ht HI
soda lime

RedP/
1. ,

2.

cuz a
hydrocarbon ,

a
hydrocarbon .
 am
Q .
A ( CAH , og Bt + Caq
I, ,
-1
yellow ppt 1. H
'

Focus on (A) : 2. Red

must have :
E V2
D
'
THI
☐

CHZCH -

Ion or
cuz -

g
-

f
o

,
can't be
of a ketone
!! Cnltzno
Cn Han -120 alcohols
/ ether
4 I ??
04
g- 2° methylated
.CH#H-CHzCH3
Sec -

butyl alcohol
cnz-Ehcyz.at , cuz -42043 NaOH
Iz

I Isc
§ -92043
CHI
←
-

>

yellow +

cHzcnz§→Na Ht
CHZCHZCOOH
Redp
2°
B" HI

Chzch -043 °
cnzcnz.CH ,
I
Br
T
 Which
compounds give + ve
Iodoform Test ?

-1% -

cuz or
-

cuz
"°"
CHI
}
I .

Iz

• ☐ = H ? CH ]C4z0H ( only 2001 giving

above test)

•
☐ = R ? R -9%-043 ( only methylated 2°
alcohols )
•
☐ = Phenyl ? Ph -

§nH -043 as o)

* R-%n cuz
( o)
④ ctlz H CH }
g-
- -
c -

•
Acetaldehyde is e-be
only aldehyde giving
iodoform test
* All
methyl ketones
( Chs
§
R
) eñclnduig
- -

phenyl ; cyclo alkyl ; allylic benzylic

;
will
respond tvely iodoform .

cnz
-
É -
R observe that :

f)

NZ }
CUZCO -

cuz
-

g
-
oh

otzco
-
Ph 0

CH> co -
cnzCH=CHz OR

CUZCO
-

cuz -

☒ do not

give iodoform
Test (7)
 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
 Chemistry of Grignard Reagent
Types of Grignard Reagent & Preparation:

Ether
Rx +
Mg RMGX •
Alkyl magnesium
halide
E- iñgt I
io.me
-

(Polar> covalent
Types : R -1-4 ; Alkyl ; cyclo alkyl ; Phenyl
allylic ; benzylic (PhMgX)
[ vinylic
aekynyl RC mgx
: c-

: HzC=CH Mgx
-
 Polar Photic MEAS
-

=
Role of solvent :
1- polar
Aprotic = R -
O -

• Polar Protic :
Ñ- 4%4 Ry
t acid-base
carbanion

as base as Nui

GR is unstable in photic solvent

• Polar Aprotic :

GR is stable ? as there is no

acidic H -
atom
•
Why Polar : We need to solvate GR .

Contd
 St
solvation in R
-
§ -
R
Polar Aprotic :
;
solvation of
m£g+
GR
R -
-
×

←
É'

-
Rst

which is better of two ? ¢4320

B. Pr 34°C
( Etzo
)
OR
•
formation of GR is
THF
0
an exothermic process !!
B. P I 66°C
Properties of Grignard Reagent:
(A) As a Base (Bronsted Base) (B) As a Nucleophile

E- iñgx
Base Nucleophilic
Carbanion

looks for an 200k$ to attack

acidic H atom
-

or approach an

? electrophilic substrate
H atom attached Ot o
aldehyde
- -

F-
• -
°
to most electro -
ve & ketones

atom : E, ☒ or with a •
-

§ -
L etc
EWG
( ?)
acid
0
(704 or
•
c)
derivatives
As a Base (Bronsted Base): Special Cases: 1 .
R
-
⇐ c- Hot
2. % -
CEN

ÉMg% +8+2 RH 1- Mgc )× 3 .

R-q-I.tt
"

Dons ted Bronsted Alkane

base Acid Hot
( proton 4
(Proton donarj
.

acceptor

Note : The basic character of GR is dominant

over its nucleophilic character .

R' É-c=cMgBr
"
2MgBr + CECH 3h 1-
-

(Terminal only)

sphydn 'd C- I effect =

EWG
 Éss+
mggBr
art

•
R'MgBv t H -

CEN RH +
CN

-
as Nucleophile •
Base character dominates
( ?) Base
gt
8- It
Rt R' _ÑnÑgBr
RMgBr +
§+_Ñ( -4 2h +
§
-
-

amide )

( ?)
-

as Nu

R -
c -78 y
R-q=NH
-

11
-0 GO • amidateion
estabilises acidity •
resonance
stabilised
of amides ( RCONH ) ,
 s -
→ n°+4
•
RMgBr + RH 1-

cydopentadiene
has acidic -
H cyocopentadiene
ion

is extra stable
8-1
due to Aromatic
NHL
character
Note :
2mg Br RH
= -

on
2 not
/mol of substrate
has
?
oog.com pd
H atoms
2-acidic
-
* To find of Acidic H atoms in
number given
-
a

compound using MeMgBr (Grignard Reagent :

nMeMgBr + Hn Z n
9eH⑨t(MgBrZ)n
@gcompd)
find (n) collect CH4@DatST.p
0be : Volta (STP) :
given
CML)
in '
moles of I mol
city =
org
.

compd
1 11 11 =
In n n s )

Mass
Vml g. ←

In ⇐ g)
D D = =
of
22400 Tho org comp
-

n =
I
22400 (¥) ↳ Moe Mass
.
 Grignard Reagent (RMgX) as Base
Memory Map

"! "# "# "!

R ! MgX + H!Z RH + Mg(Z) X
(Bronsted Base) (Bronsted Acid) Hydrocarbon

8--1
H2S HX
RH RH

8-1 It +
R$SH H2O/H3O
RH Thio - alcohol
RH

8-1
R$C % CH R$COOH
RH RH
Terminal alkyne
-
special case

8--1

Stats
PhNH2 R$OH
RH RH
Aniline R$= 1'/2'/3'

-1 "! "# OH
R$NH2
RH
(1'/2')
RMgX RH
R'z
N 48-1 X&F
St Ot
NH3 R$CONH2
RH RH
sp1. case

E- o It
-
-

RD
D2O
÷
NH4Cl
RH

H NHZ *
①
or-1
H HC % N
RH RH
(Acidic H) special case

special case
𝓚𝓲𝓷𝓮𝓶𝓪𝓽𝓲𝓬𝓼

𝓜𝓸𝓽𝓲𝓸𝓷
𝓘𝓷
2𝓓

ℙ𝕒𝕘𝕖 ℕ𝕠. 𝕷𝖎𝖌𝖍𝖙 - 𝕽𝖊𝖋𝖑𝖊𝖈𝖙𝖎𝖔𝖓 & 𝕽𝖊𝖋𝖗𝖆𝖈𝖙𝖎𝖔𝖓