Alcohols and Phenols : -

when a
hydrogen of aliphatic or
aromatic hydrocarbons is replaced by C- OH] group
then the compounds which are obtained are

called alcohols and phenols .

OH
R H
-
> R -
OH
Alcohol
Aliphatic Hydrocarbons
OH -
OH

☒ >

Aromatic hydrocarbons Phenol

called Hydroxy derivatives of Hydrocarbons

•• Also .

Classification of Alcohol and Phenols

On the basis of of
no OH
groups
•
- - -

I ,
t , I

Mono hydric Dihydric Tri or

polyhydric
OH CH OH
Ctg CH OH
-
-

,
-

EH ,
- OH
&H - OH
or
or CH, -
OH
-
OH

☒ you y%0H
÷ * OH
i
.
OH
 → -,

Primary ( t)
secondary 124 Tertiary (3)

Ctlz Ctf -
-
OH Ctf -

Ctf Ctlg
-
CH
,
- É%H ,
tote
OH
•
Allylic Alcohols
In this type of alcohols OH
group .
-

is attached the to sps hybridise d carbon which

itself attached to a double bonded carbon atom

Ctg = CH -

CHA -
OH → Prob -
2- en -

I -01

Benzylic Alcohols
•
:

In this type of alcohol the OH -

group is attached to the Sps hybridized carbon

attached
which itself to a benzene sing .

OH
jctk alcohol
-

→
Benzylic .

bharat panchal 92
•
Vinyl ic Alcohol :
In this type of alcohols OH
group
-

is attached to a double bonded carbon atom .

C. Ha = CH -
OH → Vinylic Alcohol .

NOMENCLATURE :

EH} 3,3 -
Dimethyl benton -2-01
(
Hz G GH CH
- - -

}
OH
↳ Hs
 " the sing
B-
{ ,=§jcH
-

OH
•
Draw
,
µ Hex -1 -
en -3-01

3- Bromo -4 methyl -

CH CH CH CH
cty.CH ,
-

,
-
- -_
,
bent -3 -
en - 1-01 "
OH
bharat panchala -

NOMENCLATURE
OF
PHENOL
 •
structure of Alcohol and Phenol group :
v2 PM 109
.

" " 'm

0 "
%
µ
c µ
.

108.9
436
.

pm
Not
The C- 0 bond length in phenol is 136 pm which
is less than alcohol due to

(d) lone is
In phenol , pair of oxygen conjugation
with H bond of aromating sing and

acquire partial double bond character -

Iii ) In phenol oxygen atom is attached to

spa hybridise d carbon .

Preparation of Alcohols :

•
From Alkenes :( By Hydration Of Alkene )
"+
O H
CH CH=CH2 + H pH
- -
-

]
"

CH ] -
CH -
CH]
Poop an -2-01
when alkene react with water in the

of acid catalysed then alcohol is formed

presence
.

unsymmetrical alkene when water

On ,

molecule is added ,
then product is formed
according to Markovnikov 's Rule .

Mechanism :
H2O + H+ → Hit
step -1
 > c- of + H¥o÷H ÷ -

§ -

if + tea :O .

stop
%
2 :
•

of Hi:O
&
+
- -

.
- -
a

step 3 :
µ H H : OH
-

& -

& -01+-15-1 Ha :O.

→
-4-4-+1%0?
+ ¥
•

By Hydro bo ration Oxidation - :

3GHz CH
=CHg ) +
&B2H > (CH] Ctf Ctf } B
-
-

,
-

OH -1311202
-

<
3kHz Ctf Ctf
- -
-
OH)
+ BCOH) } bharat panchal 92

When alkene react with diborane ( Bath ) ,

then trial Kyl
borane is formed which gives alcohol by the oxidation
of Hao, in the presence of sodium hydroxide .

From carbonyl compound :

•
By the reduction of aldehyde and ketones
Aldehydes and
ketones are reduced to the
corresponding alcohols
by hydrogen in the presence of reagent like

pt , Pd , Ni ,
Li Al He ,
NAB Hu ele .

'

{ In the presence of Ptlpd we take tea & rest

of these take QH
}
 R CHO
-

+ H2 R CH,
-
-
OH
sialeohol
Aldehyde
R R TH Pd→ R
GH R
g-
- -

2. alcohol
-

, .

OH

•
From the reduction of carboxylic acid & ester

R -

G
-
OH + GEHT É R -
CH
,
- OH +
tho
Alcohol
0
Carboxylic Acid
" A ""
R -
c :O -
R
'

+ 4TH] > R CH, OH

- -
+R -
OH
"
Alcohol
Y ester

•
From Grignard Reagent when :

react with
grignard reagent
aldehyde and ketone , then alcohol is formed .

:c + ñ-Ñig-× >
[ orig ×]
g-
-

Adduct

> OH + MGCOH)✗
g-
'

tyo

✗ # H CH OH -

-1mg µ
Mg
-

=otR
H-gH-o.mg
# →
-

k
,
1. alcohol
formaldehyde
*
7,1=0 +

R-mgx-iR-gge-o.mg#r-cH-0H+Mg?oy A- do alcohol

# Ketones give 3. alcohol r

r%=o R-mgx-i.gs?c-omgxH--Hfy-c-0H-1Mg::..
+

3. alcohol
l

Preparation of Phenol

from Haloarenes
Chlorobenzene is fused with NaOH at
623K and 300 atm Phenol is obtained
pressure .

by
acidification of sodium phenoxide
il f- Nat ,0H
ask
#
Fj + NaOH Foam I ,
•
from Benzene Sulbhonic acid :
Benzene is sulphonate d
with oleum and benzene sulphuric acid so formed is
with
converted to sodium phenoxide on heating
molten sodium hydroxide

EI
POSH " "
"
"
%:# i ¥ >

• from Diazonium salts :

A diazonium salt is formed
by treating aromatic i amine with nitrous acid
an

( Manoa 1- HU ) at 273K -278K Diazonium salts .

are hydrolysed to phenols by with

warming
with dilute acids
water or
by treating .

1^1112 1%+6
'

Nano, 11,0
, /
2 -1116
+ Ha
" > + Na
warm

Aniline Benzene diazonium phenol .

Chloride
ofromcumenef.IN this method cymene is oxidised
in the presence of air then cumene hydroperoxide
is obtained .
Now it react with dilute acid ,

and acetone
gives phenol .

" its
OH
" 0.0-a
si
-

)
02 H+
,
, y + CH C CH}
- -

, "
o
cymene cymene hydro Phenol Acetone
peroxide
•

Physical Properties
Boiling Point :

The b.pt of alcohols and phenols increase

with increase in no .

of carbon atoms ( increase in Van

der Waals forces )
Point of butanol is more than ethanol
e.
g Boiling
.

→ In isomeric alcohol , the B. Pt decreases with increase

in
branching .
i. e B.pt follows the order

1° alcohol > 20 alcohol > 3° alcohol

[ Because decrease in Van der Waal forces
of
with decrease in surface area ]
→ The -
OH
group in Alcohols and phenols is involved
in intermolecular Hydrogen Bonding .

bharat panchal 92

§ P
pi
H H H
g
.
-

H - - - - - - - -
- - -
-

"

ÉÉ
" "
A- Solubility :

→
solubility of alcohols and phenols in water
is due their Bonds with
to
ability to form Hydrogen
water molecules .

→ The solubility decreases with increase in size

of
alkyl / aryl ( hydrophobic ) groups .

pyo
H O H
Q
g-
H
- - - -

H
-
- -
- - -
- -

H te

pm chemical Properties of Alcohols :

1. Rxn in which cleavage of -
0÷H bond takes place
2 Rxn in which cleavage of -
( ÷ OH bond takes place

# Rxn in which
cleavage of - O -
H bond takes place

10 alcohol > 2° Alcohol > 3° alcohol

it Acidic Nature of Alcohol and Phenol
a) Rxn with metal
Alcohols and phenols react with active
metals such as sodium , potassium and aluminium to
yield alkoxide / then oxides and
corresponding hydrogen .

2 R O -
-

H + 2Nd → 2 R O - - Na + H
,
sodium alkoxide
pH 4N a
1 +2 Na → 2
E) + Ha
phenol sodium bhen oxide

ima
+ NaOH →
¥1 + Hao
sodium phenoxide
b.) Acidity of Alcohol -

acidic nature alcohol is due

The of
to the polar OH bond
nature of
-
.

alcohol
☒* In f- CH q
an
,
e-0
releasing group -

GHS ) increase
the eo density on oxygen atom and decrease the polarity
of OH bond Due to this the acidic strength of alcohol
-
.

also decreases

Therefore the order of acidity of different

alcohol is as .
.

R +
Ctf -
OH >
R*
RX
CH -

OH > %-)
R
→ OH

3°
1° 2°

Q why alcohols
. are weak acid than cornball to water ?
Are In alcohol
,
alkoxide ion is
formed after removing H+
ion and in water hydroxide ion is formed after removing Htion .

But alkoxide ion is less stable than compare

to OH ion due to the of more eo density
-

presence
on oxygen atom Therefore alcohol act .

,
as weak acid than
compare to water .

H+
-

R -
O H → R O-
+

Alkoxide ion ( less stable )

c) Acidity of Phenol :
phenol is more acidic in nature
than compare to alcohol .

bharat panchal 92
Reason :
ionisation alcohol phenol
The of and
takes place as -

R -
OH
-
R -
o_0 + H -1
,

Alkoxide ion
PH
I ÷ + H+

]
Due to the
higher electronegativity of Sb hybridise d
 carbon of phenol to which -
OH is attached , eo density
decreases on oxygen . This increase the polarity of
OH bond and result in an increase in ionisation of
phenols that that
of alcohols .

In alcohol alkoxide ion is formed and in

Phenol
,

phenoxide
ion is
, ion
after removing H+ ion Phenoxide .

more stable due to resonance than compare

to alkoxide ion .

Therefore phenol is more acidic than alcohol .

g. Explain
the
following observation -

o - and b- nitro phenols are more acidic than phenol .

Au .
No, being an electron withdrawing grouts when
present at ortho and bara -

positions withdraws
co density from benzene
sing thereby decreasing the

co density of OH bond and thus make the release

of proton easier .

H -
o Ñ → Ht +
o==niI-
µ++Éy=ñ%
H
p niko phenol is
-

ni
.

>

\
O_0
0 -
nitrophenol

Also ,
the -
NO
, group intensifies the are charge of phenoxide
ion and thus , stabilise it and hence increase its acidic
strength
Éj
as "

"
^
s
<
IN 02
Hence ortho and para nibobhenol are more acidic

than phenol .
 Esterification of Alcohol -

Rxn with carboxylic acid -

O R Hao
§
HO R R
f -1011
R +
- -

+
-
- -

Aa% Alcohol .

•
Rxn with Acid chloride -

P" "dine
OR -1116
g-
a H O R R
§
+ >
r
-
-
-
-
-

• Rxn with Acid Anhydride -

+ R C OH
% _
OR
-

R
§
-

R OH + R
-

I
- -
-

R
§
-

Esterification of Phenol É CH
-
•

O - -

]
"

1¥ +
CH, -

g-
a "_% ¥1phenyl acetate (esler)
+116

phenol

É% +
as -
Ñ
!° 9,1% > §j%%0 + CH,
-

g-acid
OH

§
CH -

,
Phenol ,
Acetic

Reaction in which cleavage ? c- OH bond takes Place :

In this tube of reaction , alcohol behave as a electrophile

•
Rxn With Hydrogen Halide
2h42
R OH + HU
-
Y R Ut Hyo
- -

mixture of HU -12nA
,
→ Lucas Reagent
2h42 CH CH A
CH CH OH tea
- -

J
e- + ,
z ,
- -

} ,
Lucas Test :

1. alcohol 3° alcohol
'

2 alcohol
FH}
CH, CHI OH ÉÑ OH
CH,
{g- OH
-
-
-
CH -

HU HU
HU
\,
+2nA ,
+ +2mHz +

CH ] CH, -
-

U CH
,
-1%3 -
y
"

EH
2h42
]

+ CH,
Hao
ftp.U-tlao
-

+ Hao
Turbidity Tumidity
appears after Turbidity
appears after appears
heating 5min .
immediately

Dehydration water molecule alcohol

removing of from
is called dehydration of alcohol It is an elimination -

reaction in which cone Hasan , Phosphorous Penta oxide .

( Bos) , Alumina CALO ) is used for dehydration and

,

alkene is formed as product .

-
'

c- d- -É fc=Cf -111,0
Hasoy
ñ bharat panchal 92

The order of reactivity of different alcohols

1° alcohol
3. alcohol
'
> 20 alcohol ) .
Mechanism of Dehydration of Ethanol :

Dehydration of ethanol in the presence do conc Ha Soe

involve the following steps :

step -1 Protonation of alcohol

'

H - E I -
- in f µ-

n
I teI-
- µ

te te
Protonated alcohol
( ethyl Oxonian ion )
step -2 Formation of carbocation
H H
"

I iii. E- § E. +110
*
a- -

a- - a

n te
elimination of Proton
step -3

ctii
H H
' = + n+
+
a- c
Ethene
4 H
.

Oxidation
oxidation of alcohol involve the formation of
-

bond with cleavage of an lo H

'
bond
carbon oxygen
-
-

and
'
C H -
'
bond .

:-& o÷H He
→
Hi - > ⇐0 +

* This process is also known as dehydrogenation

Primary Alcohol It is oxidised into aldehyde which is
further oxidised into an acid .

( Hs -

Ctf
-
OH ¥ Ctg -
CHO CH, COOH -

Hao Aldehyde Acid .

 Secondary Alcohol
It is oxidised into ketone which is
further oxidised into acid

9) CH -
OH + to] %G°Hhf = o

CH
-

H2O CH
] 3103
,

<
CH, - COOH 1- HCOOH

Tertiary Alcohol
oxidised in ordinary
It is not
condition but in the presence of
strong oxidising
agent a mixture of carboxylic acid is formed
,
.

Dehydrogenation :

Ctf % CH CHO +
H2
-

CH, -
-
OH > ]

(B) CH - OH ÷ , MY
"
-0 1- H,

CH CH
, ]
'

In case of 3°
§
"

it
"
, Cee alcohol, dehy -

→ Cfg -
dration takes
CH
f OH
-

-
-

}
CH
↳ Place .

Rxn due to -
OH group of phenol
bharat panchal 92
•
Rxh with Ammonia

E
%%+H,o
"

+ NH} ¥
# 2nUq
Aniline
 •
Rxn with zinc Powder -

+ 2h A- + 2nd
yo
Phenol Benzene
•
Rxn with phosphorous Penta chloride CPUs )

got
+ Pus >
( + POU, + HU

Rxn due to benzene of phenol

ring
Resonance in phenol

As a result of resonance ,
electrophilic substitution
Rxn takes place at ortho and bara position .

Nitration OH
"

§
I
dit -

278.288¥
HNOB
""
+ €1 '
b- niko
Phenol
NO ,
phenol 0 -
nlihobhenol

%
PH " NO,
conc HMO ] -

, O 2,4
,
6- Trinitrophenol
¥ ,
( Picric Acid )
Notch The ortho and basra isomers can
Nibobhenol is
be
steam
separated
volatile
by steam distillation o
-

due to intramolecular H -

Bonding ,
while b- nitro phenol
is less volatile due to intermolecular H -

Bonding which
causes the association of molecules
"
ii.
Ho -
E- No . . ..
Ho -

TIN . .

0 - Nitro phenol b- Nibobhenol

( intramolecular H -

Bonding ) ( intermolecular H -

Bonding )
Kolbe 's Reaction
Phenoxide ion is more reactive than
phenol towards electrophilic sub . reaction Therefore .

when phenoxide ion react with co

,
, then salicylic
acid is formed as a product This .
reaction is called
Kolbe 's Reaction
OH PNA
it COL
- COOH
-4
NaOH
,
ii ) Ht
> Lot
Sod Phenoxide 2- Hydroxy Benzoic
Phenol .

acid
( salicylic Acid )
Reimer -
Tiemann Rxn
when phenol react with
chloroform in the presence
of sodium hydroxide
then salicyl aldehyde is formed as a product .

This is called Reimer -

Tiemann Rxn .

Na ima
go area
jcH0
CHU NaOH NaOH

[
+
}
,
,
,

Enter
a

011 mediate
"" OH
1¥
H -

f
Salicylate hyde
Halogenation in
when phenol react with bromine the

presence of Csa , CHU or cclu at

low tents ,
then
,
ortho and bara bromo phenol is formed .

OH
PH
I BI,
phenol
+ Br .

0 -
Bromo
Egg ,

phenol b- Bromo
OH OH phenol

BI-
Br
I + 3Br, →
2,46 -
Tri bromo
( AG ) 1
phenol
By
.

Oxidation :
oxidation of phenol in the presence of air with
chromic acid ( Nair,0z + Has 0*7 form benzoquinone

N%%°7
+0, > Benzo
tf Soa
y quinone
Ethers ( R -
O R -

) bharat panchal 92

• The general formula of ether is Cntlan -1,0

•
In ether two alkyl grouts are attached with the both
side of oxygen atom R O
- -

o Ether is also known as Anhydride of Alcohol ..

R OH + HO R → R O R + Hao
- -
-
-

Ether (
Anhydride of Alcohol )
Types of Ethers
'
,

simple ethers mixed Ethers

'

CH O CH
]
- -

]
0 -

↳ Hs - O -

CH
, , ¥-0 -
CH
,
,
Common & IUPAC Name of Ethers

structure of Ethers :
The bond angle btw ( c- %)
is 111
'

due to repulsion between alkyl grubs which

,

are attached to oxygen atom

141PM
1.
CH
CH } ,
111°

Preparation of Ethers
•
By dehydration of alcohol
Has 04
CH CH, OH
y CH2=CH2
, 443K

112504
> ↳ Hs
-
-
O -

↳ Hs
413k
 Mechanism
The formation of ether is SNL involving the

attack of alcohol molecule on a protonated alcohol .

(f) CH
]
-

Ctf
-
'

H+ → CH
}
-

CH
,
_⑦É -
H

( iit CH CH -0 : + CH] -

Ctf ?ÉfuH CH] CH

§
, , →
Ctf Ctf
-
- - -

, ,
T
H
H
-11120
( Iii ] CH] -
CH
, -¥ -

Ctf Ctf - →
CH CH -0
Ctf Ctf
HIM
+
-

, ,

•
Williamson synthesis
when sodium or potassium alkoxide
are healed with alkyl halide then ether is formed
,
.

takes place by SNL mechanism

'
R X -
+ Ri -
O -
Na → R -

Q -
R + Max .

fth
•

, Ctg
NABO
CH
f- :O Nat + Ctg Br → CH § C CH +
-
- - -
-

, ,
,
{H]
.

CH]

In case
of 2° and 3° alkyl halides , elimination completes
over substitution If a 3° alkyl halide is used .

an
alkene is the only reaction product and no ether is foamed

it ]

-141011
CH -
C -
Br + Nat -

Q - CH
]
→ CH
,
-
G- CH
,
+ Na Br
3
, EH]
4^3 bharat panchal 92 2- Methyl propane

phenols are also converted to ethers by this method .

" ""
°"
"+
A- Nabs
+ Ctf Ctf Br -
-
+

Ethoxy benzene
sod Phenoxide
.
Physical Properties of Ethers

Ipi methyl ether and diethyl ether are

gaseous and other
•

ethers are liquid in nature .

•
7 Ethers are
lighter than water i. e density is less
than water .

volatile in nature
•
) Ethers are highly .

•
) solubility ethers are partially soluble in water
and are
highly soluble in chloroform and Benzene .

a)
Boiling Point
The b.pt of ether very less than is
compare to isomeric alcohol because in ether
intermolecular is
H -

Bonding not present .

The b.pt of ether is similar

to the molecular wt
of alkane
.

Chemical Properties
it Hydrolysis
↳ 0s -
O -

↳ He + Hao , & ↳ Hs OH -

Tsonga
'

Rxn with Acids

i; Halogen :

HI ? H Br > HU 7 Hf
bharat panchal 92

# Reaction with HI :
react with HI in
when ether
hot and cold medium ,
then different product is formed
H -
I

↳ Hs -
O -

GH g- IF 2 Calls -

I 1-
Hao
I -
H

H I ¥ ↳ Hs -
-
OH + ↳ Hs .
-

I
↳ Hs -0 + GHG
ethyl alcohol ethyl iodide
Note
when one
of the alkyl grouts is a tertiary group ,

the halide ion is formed is a tertiary halide .

FH] fH]
CH CH, 1- HI CH ] OH -1 CH ] C
f O I
- -
- -
-
-

CH
,
dig
•
Electrophilic Substitution Reaction

OR group is ortho and bara directing .

Therefore
electrophilic substitution takes place on ortho
and para position of benzene ring .

bharat panchal 92
✓
•
Halogenation
PCH] PCH]
PCH] Br
Bra É%
-
+
+
acid '
o .
Bromo Br
Anisole
Anisole b- Bromo Anisole
(major )
r• Nitration
OCH ]
PCH]

1T¥
""
É , +
cone .

Have
0 - Niko ,
Anisole b. Nitro anisole
v0 Frieda craft Reaction

Alkylation
PCH ]
" "9

+ ago
¥1 +

( 52 kHz
2- Methoxy
4- Methoxy
.
toluene ( minor , toluene
•

Acylation cmajor)
' PCH] PCH]
+ CH Coo
,
← coats +
AIU] '
COCH]
2- Methoxy
4- Methoxy
acetobhenone acetobhenone

thank
YOU