Alcohol(s), Phenol(s), Ether(s) & Glycol(s) Class 7

Properties of Phenol
(A) Reaction of Phenol due to -OH group:- ③ Reaction of phenol due to

benzene
ring
( SE )
1. Acidic Nature & Corresponding Reactions
2. Esterification
3. Formation of Ethers
4. Reaction with Phosphorus pentachloride
5. Reaction with Zn dust
6. Reaction with Ammonia
7. Oxidation with Potassium Dichromate in Acid
8. Condensation with Pthalic Anhydride
( Phenolpthalein)

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 Reactions of Phenol as an Acid

Ña 1-11-20

ÑaÑHz
Ña + NH3

8-1 € Nta +1kHz

OH

Note :
t
_
Nta + Hz
NaOH
• Roy
↳ is
✗
too weak as base
Ra Nta + ROH

]
Na
RENI ÉMÉBr
Roy
pijgpr + RH
-

ork
REE
0-CH3
+ Nz
13+-3 @
Methyl ether

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 '
'
• A phenol having 2 or more EWG ( such as -

Noz ) em

its
ring gives Naltcoz (evolution of CO2 test .

H H
H
- N°2 - N°2
< yz.co , g < 02N _ _ N°2

02 I 34,6 TNP
•

Increasing acidity → N°2

( Picric acid )
•
will give Naltcos yes
very strong acid
test as it is
now
stronger acid
( pKa v1.01
)
than 11203

Note : Ron
Nao "
x
Nam
Ph -5 Nat
; on
-

NA NOH 3
RCOOH
NaOH
No Axn
?
" • 1+03 ;
weaker acid
coz ↑ + Roof Nat Phon is

sod Alcohol(s),
.bicarbonate ₕydᵣₒcₐᵣbₒₙₛ
Phenol(s), Ether(s) & Glycol(s)
than Mzcoz
C̲ i ̲r ̲c̲l ̲e̲
2. Esterification
0
> Px É
04 + R -
C -
Cl R -
-
o -5¥ + HCl

( Nu
-
addn -
Elimn )
•

(Phenolic esters)

R Ph
12-1%-0 §
R
+ o
q
- - - -
-

0
+ RCOOH
•
Phenolic
Note : ester
OH + c- CI
py

O
Benzoyl chloride C
-
- -

⑤ chotten -
Baumann Reaction ) phenyl benzoate
↓ ↓
Aromatic aromatic acid halide
alcohol = Phenol =
Benzoyl

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
3. Formation of Ethers

◦ u
a '° "
Ekta : a
good
Nucleophile
( weaker base
)
RX

SNZ
SNZ
L
phC4z- ×
d EtzS04
-

OR
sNz

OELIE-o-cuo.EE
( phenetole)
Ethoxy benzene

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
4. Reaction with Phosphorus pentachloride

OH + PCIS Pod t CI + HCl

]

(poor yield
on + POO i
}
p
0th
2h0 0th

(Ph -073-10--0
Tri phenyl
phosphate

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
5. Reaction with Zn dust

2h
OH
dust benzene

OH

C6HÉ <
43
cuz

2h
°"
COOY
@
, P, )
M CGH# dust
COOY

°"
/ CHO
C6H¢
CHO

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
6. Reaction with Ammonia Ctmmonolysis of phenol )

I H]
-
OH
Cu salt
-

MHz
50 atm
200°C

A-1203

NH
} ;
-

ɵ AT 203 MHz

+
• .
Alzoz
NHZ + Hzo

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
7. Oxidation with Potassium Dichromate in Acid
OH KMn04/ HE

No oxidn ? No oxi disable Ñ '

atom

we use strong 0A : KzCrz0 >/ H -4A

2-
84-1 zcr
> +
+ 4420 1- 2kt -13 [ 0]
Crzo >
°
Crzo >
2-

crzoz + 310] 1- kzo

0
OH Benzo
p _

quinone
(O)
( p Quinone
-

↑
(Bright yellow crystal )
Kzcrzoz 0

(abnormal oxidn)
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
8. Condensation with Pthalic Anhydride
OH 0

Conc .

2 + (→ 2°)
Naso,
0

(phenol ) ( ptnalic anhydride

- (Phenolphthalein)
(Pink u

colour ) alk 04

OH

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
(B) Reaction of Phenol due to Benzene ring:- ( SE Reactions)
1. Halogenation Br
-1

2. Nitration NOT
3. Suphonation 503

4. Nitrosation Not
5. Alkylation 12+1120=8 :
poor yied [ F- C alkylation/acylation]

6. Riemer Tiemann Reaction 8 Cclz

7. Kolbe’s Reaction Coz

8. Reaction with Aldehydes & Ketones ( Protonated carbonyl compds)

* = 0+4
(C) Chemical Tests for Phenolic Compounds

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Reaction of Phenol due to Benzene ring:-
1. Halogenation (Bromination)
OH OH
OH
Br
Brz →

Br -1 +
csz

phenol : -1M > I

0 -
Bromo phenol for
( major
-

strongly activating
•

Up directing
-

Brzlcsz / Brt
◦
; Brz Fe
; Brz / Acoy ; Drz/ Fear}

• Bra / → Brt %
Hzo :

i.
E- 8- +
-
_ _
.

hybrid
.

Consider
, .

=
resonance ;
:-. "
Phenol :( n' a
of
.

)
. . .

-1M
←

effect ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 OH OH
Brz Br
Br • 2,4, 6- Tsibnmo phenol
H2O
(acidic)
(24,6-11310)
H+
ppt ↓
-

Hzocaq) Bo .
White

(Test
-1
- Br ? of Phenol)
◦
•
( high concentration)
• = strongly electrophilic

(phenoxide)
4
very strongly
activated

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

Br
:0H OH
µ

Brt Br -
HBR

2021420
OH OH
Br Br -1 Bst Br
Br

-4136 -4136
0
bsomophenof
-

Br

* Alternatively :

Br
OH 0 Tautomerises
µ µ OH
Br
Br Br

HBS
(keto form)
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Visualise formation of products :

OH OH
CHZ Brz Br CH3
H2O

Br

OH
This Br(Br+) Fuids
OH
very difficult to
Brz Br 6
2
Br enter
.

> [ Why ?)
H2O ↓
CMS 5
3 cuz due to steric
¢
Br crowding at

OH
£ '
(2) postion
OH
Brz ↳
Br Br •
yield is
low
H2O very
Chz
Chz

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

1. OH OH
COOH Brz Br Br
+ coz 1- H2O
H2O
34,6 TBP
acid
0 -

Salicylic Br How ?

ipso substitution

aq medium

° " OH ◦

E-
•

_
◦
-

-
E -
o
-

+ Brt Br -
Coz ↑

(ipso)
0 -

Salicylate ion
OH
OH
-1 3r
Br Br Br -1 Br .

Alcohol(s),
Br
ₕydᵣₒcₐᵣbₒₙₛ
Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
2. OH
Note : The substituents
OH
should be Acidic
5034 Brz Br Br
Coon
group : -

µ + 503
-

5034

+ H Br
Br
aq .

0
-

0 0
-

° " : OH 0
OH
5oz s 5=0 + By
-1
5=0
>

( ipso Br

503 ↑
-

OH
OH
Br
-1
Br Br Br -1 Br

Br

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
2. Nitration HNO3142504 Ñoz :
strong electrophile
(c) (C)

OH OH

OH
HN ) _
N°2

|
" "° " +
""
I
Noz
Ñozci " + ] ]

Alas

'
ÑO Ñoz d' '
14205 = = + p
,

Aldz Nitro -

phenol
HNO } (C)
OH

0am N°2
Hz 504 % yield is
poor
(25-307)

( Picric Acid)
No
,
•
How to
Alcohol(s), ₕydᵣₒcₐᵣbₒₙₛ
Phenol(s),
prepare Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Picric Acid in Good yield ?
 OH
3. Suphonation HzS04 5034

25%
OH 0 -

hydroxy
sulphuric acid

OH
HzS04

( 100k) p
-

hydroxy
sulphuric
Hz 504 acid
5034
( 2. oeq)

OH
5034

5034
ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
Manufacture of Picric Acid
OH
OH
5034 HNO3/
(c) 42504
Hz 504 µ,

( 2. oeq)
ÑOz (excess]
5034
OH Ñioz OH
02N 5034
strong 02N Noz

ÑOz( ipso )
5034
Moz
11102 ?

Ñoz Ñoz
503^1 -503
-

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
4. Nitrosation Ño : Nitrosonium ion

: a
very weak electrophile
NÉCT ↓
>

OH
does SE Rxns only
in Phenol

OH

Na N°2
>
Ñ0 •
p -
Nitroso
no, Phenol
4=0
E HNOZ

O -
H O

4=0 V -

o -
n

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
5. Alkylation & Acylation F.C. Alkylation & Acylation give
a
poor yield
OH

RCI EH
AIU> Alds
Rcl

Alds

Rt At +0-4
pic

OH
OH
Rt
or RC=É
I
R -
{ •
yield is
poor
R
• Since +0 deactivate
nñg
'
'

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) p is Possible
•

product C̲ i ̲r ̲c̲l ̲e̲

8. Reaction with Aldehydes & Ketones Is this reaction an SE ?

OH
H+
+ H-c=É HzC=ÉH
'
n

Hzc
-0+4 on
HzÉ -04 :(an electrophile)
OH
+ - CUZOH
{ 4204
ÉH
+04
y
0+4
'

+
cuz __

CUZOH

ₕydᵣₒcₐᵣbₒₙₛ
Alcohol(s), Phenol(s), Ether(s) & Glycol(s) C̲ i ̲r ̲c̲l ̲e̲
 OH
RCHO
R-cu=n
ht
Electrophile

R -cu=n OH

:(major)
'
'
p
R -
CH -04 '

O'
+ ( minor
OH

Me
+ Me
.
µ -1
c. =D →
C=ÉH : Electrophile
Me
Me
On Me
Fae
+ 6=0+4 HO C
,
-04

Me Me

ₕydᵣₒcₐᵣbₒₙₛ
'

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

'

p [ Major)
IMP
C̲ i ̲r ̲c̲l ̲e̲
:
Friends
.
! We will do Rxn : 6

Rxn : 7
in next class
A
°

humble
request
°

I
: Please read chemical
Tests of Phenol ( ie)

groups
1-
✗
Page . . . .

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
"
•
6611-504 + Feltz [ Fe(C6Hs%] -1344 +34-1

Phenolic
2 .

compounds :

+ Colts 'Ñzci / on ( pH
-

> 7)
(0-57) ange
coloured

dyes

Phenol B- Napthol
✗ -

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

Phenol ink Green

1-
Nap -1h of
•
•

• 0 -
Cresol Zed •
2-
Napthine light Green

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

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