Alcohol(s), Phenol(s), Ether(s) & Glycol(s) Class 8

Properties of Phenol-2
(B) Reaction of Phenol due to Benzene ring:- ( SE Reactions
1. Halogenation
2. Nitration
3. Suphonation
4. Nitrosation
5. Alkylation
6. Riemer Tiemann Reaction 8 Cclz

7. Kolbe’s Reaction CO2

8. Reaction with Aldehydes & Ketones ( in presence of H -1)

(C) Chemical Tests for Phenolic Compounds

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
6. Riemer Tiemann Reaction
OH

OH CHO
-1
NaOH Chaz H

or KOH Naoki 60°C

o -

salicy / aldehyde
( Major)
OH

NaOH
f- p -

Salicyl -

aldehyde
0
-
•
exerts + I
effect over
1 (Minor
the activate
sing ; this will CHO

-0 ' '
'

position more than p position

5 activates most highly activated
: the ring
•

benzene Ning for SE reactions

molecular 4-
• 0 -
Sa /
icy / aldehyde show INTRA -

bonding
( chelation
)

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 8-1
H '

g-
intramolecular H
bonding
-

C stabilise '
'

u o
product

Visualisation of Riemer -

Tiemann Reaction :

E.) Acid -
base Reaction

OH
oÑa
NaOH : Phenoxide ion

or KOH

420
-

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
I. Generation of electrophile :

8-1

H ¥ C- highly stable carbanion

C
-93 Clz :
-

base
( ?)
-

H2O
A-

Di chloro carbene
_

.
-
:
coz * Cl

. Free radical : as an electrophile

II. SE reaction

+ : Caz ?

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
0 °
5 n

+ 8 Cclz
E- Cl
di
o
E IMP-1
4
-04
CHAD ,
d- a
Nu di
( gem - di
halides
SN
gem did
-

0
OH
CHO H -1 CHO

H2O
(acidification

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
How to visualise formation of p -

Salicy / aldehyde ?

5
0

: cdz

O
-

OD -
T

E
C-
H Clz
-6

CHC /
z
cnclz
OH

on H+

(Nu) -

Uzo
CHO

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
7. Kolbe’s Reaction

H
H
-1
NaOH coz H COOH

T = 130°C

P = 6- latus

NaOH
0 -

salicylic acid

' '
+ p

Is
-

11 É c. -1
C = 0

8-1
-0 : keto

§ form

H
H
o
-
-

o
f- (Tautomerisation
Ht 11
9-04 0
◦
end form ( extra stable
)
(o salicylic
-

acid
)
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 OH
Reactions of Salicylic Acid: ☒r Br

[
.

Brz / H2O White

•
ppt
Test of Phenol
•

B2

CH-304
OH 0
"
OH H -1 C O
cuz
-
-

-
COOH •
Methyl salicylate
oil
•
of Wintergreen

salicylic &
acid OH
11
Ht _
-
oph
•

Phenyl salicylate
• Sal of

É
0

(anhydride) cuz I -0 cuz/µ -1

10-12-93
-
- -

COOH
-

-
OR

( Aspirin)
(acetyl
-9,0-4 / Py
chloride)
cuz

(Acetyl salicylic acid)

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Chemical Tests for Phenolic Compounds
Felts
1- .
Phenolic
compounds different types of
Neutral
colours - - - - -

Feels
Phenol violet coloured
Neutral
>
complex
3-
Fe ( (611-506
3-
+
•
6811-504 1- Feltz [ Fe(C6Hs%] + 344 -1-34

2 Phenolic
compounds :
Colts 'Ñzci / on 7)
+
( pH
.

>
-

(0-52)

angel I 1
" "" "

dyes

,
Phenol ← na,
✗ -

Napthanl

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
3 Phenolic Pthatic
anhydride Phenol
.
compounds : 1-
/µ+
alkali 42504
(Phenolphthalein
conc .

Phenol ink Green

✗ 1-
Nap -1h of
•
-
.

0 Cresol Zed
Naptnol light Green
13-2
-
• -

• in -
Cresol violet blue Resorcinol yellowish
cresol No Rxn
04 green
◦
p -

OH
4. litmus Test :
blue
phenol Red
litmus
( acid)

5. Bromine water test :

3k
Phenol 74,6 Fri bromo phenol ( while ppt↓)
µ,
(TBP)

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Electrophilic(Aromatic) Substitution reactions of Anisole:
:
cuz
-

)
: -
Orne : -
I < + M ◦ Me :
Activating
( mildly)
:
Otp directing

Ñlclz
+
Note : Eme 1- Along -

FC reactions slow
are
very
giving poor yields .

Note However Anisole brominating

:
gives :

Nitration

Sutphowabon

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 -

Me -

Me
-

Me

1¥02 / N°2
+

I
N°2

BE -

Me -

Me

Br
+

'
Br

Me
-

Me
503
-

5034
+

5034

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Claisen Rearrangement: (Allyl phenyl ether) :
Intramolecular CSE type)

-
H -

cuz
-
CU =
Cuz

NaOH
CH Br
+ cuz = -

C4z-
allyl bromide
allyl phenyl ether

3 2 1- H
3
-

Cuz
-
CU =
Cuz z z

C4z- Ch =
cuz

200°C
§ -

allyl phenol)
3

cuz 2

Cn H
11 2 2 3
1
CUZ cuz
-

CU =
Cuz

H
keto
1 2 3

form cuz
-
Ch =
cuz

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 '
'
Note In Claisen No product
:
rearrangement ; p is

cn=n formed .

0
cuz
- -

OH
- Me 200°C 14
cuz __ Cuca, - Me

0 -

cuz
- cn=n 2

Me
- Me 200°C
No Reaction

0 -

cuz
- cn=n 2
04
14
Cuz CU =
cuz
-

-
-

200°C

1
I
Me ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s)
me
C̲ i ̲r ̲c̲l ̲e̲
* Read Module : Alcohols

Glycols theory
Ethers →
Physical Prop .

Phenol → IN -

Chapter excise

ch'st : _

Attempt
1. Revise class lecture Illustration

2 .
Read Module : Theory
I
INE
Illustrations
3. HWS ( all
I
[ class
summary
(5-8 Pages)
Workbook : level -0
/ Level -1
/ Level -2

After 1-1
II. one week
Alcohol(s), : ( Tee Mains
ₕydᵣₒcₐᵣbₒₙₛ
Phenol(s),
1 ,

Ether(s) &Different
Glycol(s)days
Archives)
z
C̲ i ̲r ̲c̲l ̲e̲
-
Hydroxy Acids : Cn Hzn -03 : 913,8 ( or
8) hydroxy acids
^

CHZOY Acid
[211-403 :
{ OOH
:
Glycolic

B ✗ ✗

C3H60z : cnz
-

cuz-004 ; cuz
-

CH -0004 :(Lactic acid )

bn on
'

in 13 2
13 ✗

C4H6O3 : Et -
Ch -
COOH j CU ] -
ch
'
-
Cuzco 04 ; cuz CUzcnz.CO 04
-

✗ '
on on

Action of hot conc .

42504 :

OH
H+ Di esters)
du Lactides (
-

2 R
•
- -
Coon
✗ 40 -50°C

B ✗ Ht
R-cn-cnz.com X P -
unsaturated acid
,
•

ton too ,

lactones
R-tu-dnzcnz.com
•
r -

on
'
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 2 R -
ca -
É ii :
H+
R -
CH -
C=0
40 -50°C
big
"
, 1 ,
"
iii. .
.
0
I
◦ = du -
R ( intermolecular
⇐ c- Cn -
R

esterification •
Di ester
-

.
Lactide

R R -
Cy

= CH -
R

Lactide .

• ChzO4 Ht

Kooy 40 -60°C

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
* p -

hydro acids : p
°
B
°

µ -1
cn=Eu -4-04
,
R -
CH -
Cn -
-04 R -

(undergo dehydration 04
-
2,13 -
unsatd acid

i.

highly stable
(7)
•

conjugated [Resonance)
* r -

hydroxy acids :

p3
2
° H+
r is a ✗
,

R on &
Cn cuz
- -

40-602
-

¥
-

4 22 1
4
1 3 ;
50 •
5
R
Intra -
molecular
esterification
f- Lactone)

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 * To find number of -

0H( hydroxyl) groups in a

poly hydric alcohols
-

(via Acelyation )
ROH + Cltz
-

COCI
%
CHz -
É -

O -
R + HCl
ester [ Product)

MA = Mol .
Mass of
" Acetyl snap ¢43 -
%-) : Mof Mass.
= 43

Roly hydric)alcohol
-

Mp = thot .
mass of product (ester = 43 -1 Ma - 1

* Now consider a
Poly hydric
-

alcohol : let n = No of OH
groups
-

¢ n°+3
§
"
(
-

MA) -
-

( OH )n +
Product ( Hp)

Mp = (43h + Ma -
n )

MPz
n =

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
A
polyhydric alcohol ( X ) with
Ma -_ 111
undergoes acetylation
ester (4) with
with
acetyl chloride to
give an
Mp = 237 .

Identify the structure of alcohol ( X )

(a) .

(b) Determine the product obtained when C) reacts with

excess of HI .

Sdn : let n = No .

of -04
group : using : n =
Mp -

MA
H, 2
n :

2¥11
=

CUZOY Ch3
1 HI 1
isopropyl
1<2%2 =3
=
✗ : on -
I
cmon
£43
.

Luzon iodide .

kltsoq ¢004)z
H COO H + coz
Chz = Cn -
CHO
380k
↳
Acryl aldehyde formic acid
( Acrolein)
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
44204
I
442 { nz-T-z.gg { 2- I
"
3h1 '
' ,
Choy Cn ? Cu CU -
I
1 I I
- i -

Iz 11 M addn
-

CUZOH Cuz cuz-4

'

,
cuz

di iodide
(Tri
-

iodide)
(vicinal)
-

+
Unstable cuz
2 HI
11
Cn
-

Iz
cuz
1 1
I cnz
44
-

cuz

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 242
(3°
003
A > B No oxidn .
alcohol)
(64100 (O)
No chiral Centre
optically active

(alcohol) one
:-C _=C
group
-

↓
( Joe) cU3 Cuz
* 242 I
UC -=C4 C 04 Czlts -
C -

04
301
(A) GAS
cuzcyz
↓ Cross

( No oxidn
)

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 42°
C > 480 insoluble IMF suggests :
C6UsC4zon ;
Colts -0cm } &
iVa2C°3 insoluble
°"
NaOH
soluble Phenol C6H4{ CH]
Brz C>
450133 Soluble (cresol)
H2O in NaOH

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Illustration -13 .
Identify the product with the help of mechanism .

H> ◦ + 1. Ht
(a) CH -

C ICH

¥
=
2¥ 44
-

CECH

0h2
+
Ht

420
-

+
CH =c= CH CH -=C4
+
• benzylic
Hzo :
Stable
( ?)
-

resonance
•

CH =C= CH =C= CH
{
4
"+ 104 •
enol
n #n -
Tautomerises

CH =CH- CHO

ₕydᵣₒcₐᵣbₒₙₛ
cinnamatdehyde
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
(b)
Ht @ Ct : )
More stable

4 +2
5 3

I
H
8

6
L

&
5 3 4
5 3

2
6 Me
6 Me
-1
y
H

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 3 2 I

4
5

/ . µ -1
2. -420
Me
+7
shift
-

Me _
_

n -1 Me
+ Me

Me Me Me

2
Me
3 ¥ -
'
3 Me
" 1
Me
it
4 4
Me
5 OH
-
Ht
g-
Me
I
0

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲