NOTES BY:-

VIPRA BHARDWAT

Alcohol
Phenol
&
Ethers
AAKCCOOIHIOOLLPPIHIEENVIOOK #☒☒ EETITHIEEIRSS
Classification on the basis
of number of 011
groups
Alcohols
a.
luonohydeic → R CHZ OH
-
-

b.
Dihydric Alcohols R
GH CH 2
- -

,
OH OH
C.
Jrihydlio Alcohols →
CHZ OH
-

{ H -

OH

{ Hz -

OH

}
Primary R cuz OH
- - -

secondary R CH OH
- -
-

£
Tertiary
-

↑ sp3 hybridized
r on carbon
g-
-

Allylic Alcohols → R CH = CH CH z OH
- - -

Benzylic Alcohols →

f) cuz OH
- -

}
" → R CH CH OH
Viuylic
=
-
-

Phenol →
9" spa

Preparation Of Alcohols :→
• acid
by catalysed hydration [ Acidic Hydrolysis ]

¥
F. =
CI + iizo
% -

%
" OH
Mechanism of Reaction ( Markiuov Addition
step I → Protonation
of alkene to
foehn carbocation by
electrophilic attack of 1130+1 Ht
step 2→ Nucleophilic attack
of water on carbocation
Step 3 → Deprotonation to form an alcohol

•
by Hydrob ovation oxidation [ Anti MK
]
R -

CH = cuz
¥ R -
CH -
CH z
11202 / OH I
-

H GH
•
from carbonyl compounds
Reduction & ketones
of aldehydes
•

R H / R NÉE d
§
-

R
-

-
-

HIR
line Hy 1
'

Oh OH
H2 / Ni
Aldehyde / ketone
1° Alcohol
Aldehyde
→

ketone → 2° Alcohol

by Reduction
of carboxylic Acid and Esters

[
•
NABHY only
Reduce

r -

o -

on ¥4s R -

cha -

OH
Aldehyde
and
Ketones )
É
'

5-
'
R OR

§
R + R
cry OH
-
-
-

OH

Ex : -

% -90 É CHZOH
>
CH +
cuz -
} on

From
Grignard Reagents
•

[ 09
R'
'

H H 1° R cuz OH
C
Mgx
- - -
-

+
11
0
 lil
R' [2]
Mg ✗ R CH OH
R C H
- -
-

+
-

11 I '

0 R

[ 2°] ↑
R R'
C R + Mgx R
f 011
-
- -

"
o r
ketone

Physical Properties
B. P & M -
wt

carbon ↑ B P ↑
no
of
-

B P-
x l

Hing
Ethanol and Propane have
comparable Molecular masses but their
boiling
points differ is intermediate
widely The B P
of Methoxy methane
of
-

the two
boiling points .

Ethanol -

Costs OH j Propane
-
c.
3118

OCH} > C 3118

Coy 115 OH > CH3
↓
H
Bonding
-

The thigh B. P
of alcohols are
mainly due to the presence of intermolecular
in them which in
hydrogen bond is
lacking ethers and Hydrocarbons

SOLUBILITY
Solubility of alcohol and Phenols in water is due to their
with
ability to form hydrogen bonds water molecules
as shown
1-
H
bonding
H -

O - -

H - -
O
1 1
11 R

The decreases with increase in size of alkyl large

solubility
[ hydrophobia] groups .
 CHEMICAL REACTIONS
Alcohols both nucleophiles
acts as and
electrophiles
Alcohol as nucleophiles → bond btw O -
H is broken when
when alcohols react as nucleophiles .

R -

-[
E -

H +

.
→ R -

¥ & -
- → R -

o -
e + Ht

Protonated alcohols blue C- 0 is bookers

as
electrophiles : bond

when they react as

Electrophiles
R -

OH 1- 1130
⊕
→ R -

0%2
Protonated
Alcohol

R -

0%2 + ✗
⊖
→ R -
×

Reactions
involving cleavage of O H bond [ Nucleophile]
-

1. Acidity of Alcohols and Phenols ☆

2. Esterification ☆ ☆

Reactions
Involving cleavage of C- 0 bond
/ Clean
penile ]
with
1. Reaction
Italics [ Lucas Reagent ] Hx ☆☆

2. Reaction with Phosphorous Trihalides [ Pxz ]

3.
Dehydration [ -1120 ]
4. Oxidation ☆

Alcohols Phenols Alcohols &

Acidity of and .
: -

Phenols react with active metals such as Na,k

to
yield alkoxide /
and he
Phenoxide and
corresponding
hydrogen .

3 R
-

OH / Ph -

O -

H + Al → All OR } +
3-2 Hz↑
Acidity of Alcohol
anion ✗
Acidity ✗
stability of conjugate Ma I -
-

tis
 R

R -
d -
811 < R -

ca - % < R -

CH, -8114 CH } -0%

£ £ 1° 0°

3° 20
Phenols react with aqueous NaOH to form sodium
phenoxide but alcohols dont react .

R -

OH + NaOH →

Nat
-

PHOH + NaOH →
Pho + Hz 0 .

Ph OH > H2O > R OH -

Acidity older }
iii ]
Acidity
TOH
of -
◦ 10¥
ipnenols^
no, it
'
0

× Yrs c> A > B

A
④ Noz
H
/ TI -

Esterification Alcohols and phenols react title

carboxylic acids acid chlorides and acid

Gantry
,

foemesters-yr-c-o-fr-cg.ee
decides to

If
R C

§
O R
- -
-
-

"
◦
 Ctlz CHZOH + OH C CH }
-
-

11
O

CH
} CHZOCCH } + H2O
11
0

Ethyl eihanoate

Smp Reactions
É
☆ .

p 0 CH }
-
-
-

I
^ c- OH
CH
}
-

C -

→ - Coote

10 1- " +
:
+
o v
OR Aspirin
salycyeic
acid C. Hz C O
-
- -

8
Reaction with halides
lucas
Hydrogen & Anhydrous 2h92
Reagent [ come Hce
-
.

R -

CHZ -
OH + L R -

no Reaction

R OH 1- L 2 2- 3min
CH
'

- - →

k Turbidity
a
RX

R -
§ -

OH + L R
.
- 2- 3sec
'
r
Turbidity
RX

2. Reaction with Phosphorous Trihalides

R OH-

+ Pclz - R Ut -

HzP03
Dehydration C- 1120)
C. 2115011 ¥4 CHz=CH2 + H2O
443K

911
CHZCHCH } 85%113-7 ctlz
-

CH =cHz +1120
440k

CH}

d- 1412
CH 3- OH
20%-113%04 cuz -
C -

CH
}
+
H2O
I 358k
CH}

: -3° Alcohol > 2° Alcohol > iaecohol

Reactivity
Mechanism : _

Step 1: -

Formation Of Protonated Alcohol

Step 2: Formation of carbocation

-

Formation of ethene by elimination

step 3: -

of a proton
Oxidation

it oxidh

q
O H →
7=0
- -
-

3°
go R

R -

CH -

OH R -

C④ -
o ④
-
R -
d- OH
ti k
↓
¥
/ ] ↓
↑
niece R 5- OR ketone

§ / oxidising
-

"
- -

no oxidation
Always [ His Absent ]
agent
↓ strong agent
R - -

OH
 Strong oxidising agent →
Kmnoy , Kzcrzot ,
G. 031-1120
↓
Hzcroy
Mild oxidising agent
→ PCC
[ Pridinium
Chloro chromate ]
Preparations of Phenol

a. From Halo arches [ Dow 's Process ]

ie qua
+
Natoli ¥

b.
Benzene Sulphonic acid

E¥⇐E¥÷ÉÉ
150311

£25207 ¥%ᵈdro lysis >

[112504+503]
c. From diazonium

ˢᵈᵗ¥%ᵈ
1MHz
1¥
"

Phenol
d. From Cunnane

¥;
"

→
i
Iannone]
%
+%=o
2
Methyl propane

✗ £3
ketone

Reacti-ofphenol.PHPR +m

it ( OR
oelhodpasa

Electrophilic aromatic substitution

1) Nitration
"
10h PM -7475m
"°÷
/\
I
die HNO }
→
+
For
×
y
[ Noz
tow
more
B- P ,

Intel volatile
B. p↑ low
molecular ,

H ◦
volatile

Bonding
[ strong ]
?⃝
 "
"
Nk

HN 03 0

IN 02
Picric acid
2. 4,6 Trinitrophenol
-

reaction is carried
Halogenation → when the

out in solvents of low

polarity such as

CHU} or Csz and at low Temperature

" "
i i
G-
Be

+ Bra ¥9 +

I
low
Temp .

"

¥ I
# When Phenol is treated with her
Bromine water 2,4 ,
G- Tri bromo phenol
is formed as white precipitate

B
pH
Be

313ha
☒
→
+

be
 Kolbe 's Reaction

i
"
PNA

" I ÷ .

2
Hydroxy benzoic
acid
[ Salicylioacid
]
Reiman Teimann Reaction

f-
Nat

¥-404
Chloroform / 11¥ %
" ↓ NaOH

1° pivot
"°

T_
on
c-

Salic
aldehyde
Reaction phenol with zinc dust
of

+ on →

☒ + ZnO
 Oxidation
i

Éii A
¥
0
Benzo quinone

ETHERS
Alcohol
a. From
Dehydration Of : -
Alcohols
undergo
dehydration in the presence of protein acid
( 112504 1113 POD
⊕
R C Hz OH R CHI OH
¥ R CH z OH
-

t
-
-
-
-

↓
SN 2 mechanism

R -
C Hz -

O -
C Hz -

ether
The
bimolecular
formation of ether is a nucleophilic
reaction CSNZ ] This method is
.
suitable
of ethers
having primary Alkyl groups only
Williamson synthesis → An imp laboratory . method

for the
preparation of symmetrical and
unsymmetrical ethers .
When an attire halide
with
reacts Sodium Hydroxide ,
ether will
form ,
this reaction is known as Williamson
Synthesis . Mechanism → SN 2

R -
✗ + R -
Nta → R -

§ -
R + Nax

less steric hindered

 for better
note :
yield of ether
-

↳ unbranched 1°
TR -
+ R o_O → R -
O -
R Alkyl
halide
1°

CH }
CH }

CH3%
I

cuz
f
✗ t
dich
-
-

→ CH -

}
,
elimination
cuz Aeaene

Physical properties
in B. P alcohols and ethers
large difference of
•

is due to the presence of Hydrogen bonding

in alcohols

Solubility in water due to H

bonding
-
-

CHEMICAL REACTIONS
Cleavage of C O bond
-

→ both R 1° →
SNZ ( ✗ attacks
group ]
on small

One is 1° & other is

[ ✗ attacks on
2°R →
2

group]
SN
small

One is 3° & other is

/
✗ with
goes
1° / 2° / 3° Sly bulky alkyl
→ , part ]
Alkyl aryl
ethers are cleaved at the
alkyl oxygen
the stable
bond due to more
aryl oxygen
bond

40=>-0 -

No Ran

-
o

↓
✗

OH +

Order of Reactivity HI > H Br > Hce

Electrophilic substitution

→
Halogenation
PCH 3 PCH } 9913
Be
+ Bra ¥ +

be
Friedel Crafts Reaction
↳ c-
⊕
→ carbocation

fat }
10413
%
"
}
Rt

1¥
%ÉÉ¥
"

+ ¥
⇐C -
R
Nitration [ E.
⑦
→ Not ]
↳ Niteonium ion
10913
OCH }
1-
HNO } É
-
Nozt
Auriol

↑
"

¥
Noz
 e