Johol Inenot

SouranData
 H
R (Asconor)
-

H -
> R-OH
↑ OH
H On

jo]
-

+OH
H
>[] (onenor)

H
R R-O-R (Eter)
-

H >
+OR

classification (A) Alcohol and Phenot

was on theBasis
of no
of hydroxyl atom present:

I
·
CHz-OH-> Monohysic alcohol 01
I
·
CHy-CH-on- Dihydis alcohol X
Monohydic phenot
⑧

On OH
1 or
-

Dihysis wihycic phenol

M2-42 alcohol
-> ⑧ I

oh
oH or
I
-or-Trikydic phenot
CH0ny- inmudic alcohol
·
·

-
H

On the Basis
(b) of Hybridization:

sp3 hybridization:

R-c-or-> 1°
(primary alcohol)
(secondary alcohol)
R-et-op-2"
·

R
30
(Tediary alcohol)
R-e-OH
· -
·
R-CH= CH-C-OH-> Alylic alcohol
-

spy hybridized carbon attached to c= c it is

If a

called
ally carbon.

CH2-OH

· Benzyl is alcohol
->

If
a
spy hybridized carbon atom attached to a benzene
sing itis called
Benzyl carbon.

sphybridization:
·

·
U2 CH-OH ->
Vinylic alcohol
=

Halogen attached to Carbon which forms a double band

willanother carbon ->
rings carbon
On
&

↓
-
1 ->
phenot

(B) Ethel

↓ ↓
Symmetric ether Unsymetrical Ether

·
Cy-o-My ·
2H5-0-2245
Ph-0-PH ·P4-0-CHy

·
2245-0 -215 ·C548-0-CeH;
 Method of Preparation of Alcohol:

as from alkenes

acid catalysed hydration:

(i)
by
Alkene reachwithwater in presence of acid as catalyst -

form alcohol. In case of unsymmetric alkene,

↳

Markovnikoff addition takes place.

ne
Ca=CH,+H-ot -
CHy-CHG-OH.
·

4t
CHy-CH=CHG k-OH >

ets-ut-c
·
+

Mechanism: -

120 + H+ sugot
H

MICH=Ma +-!-e-cy+hi:
I

Hoot-enz--us
X

C4z-C-CH3
H20 -- Hr

si

(ii) Byhydobration-oxidation.
·
Dibarance (BH3), reachwith alkene to give kialkyl
borane as addition product. The addition of Barane
to the bond in such
double a manner thatBaron
atom
getsattached to the spcarbon carrying more no

of t-atom.

·
Mere omidising agent is Hebe
·
Itfollows antimenkornikoff rule.
 CHI-M Cy
=
+
H- s- H

01 H

↓ H
I
1 -
B -

H
>Y
CH-H-CH2-B-H t
+ ex,--te
in
I

20 20
I More stable I Even stable I

P
CH-CH= C2
↳
CHG-CH2-CH2jB
"D
5= c2
CHG-CH2-CH2)-B
:
[CH,CHG-CH2) -
B -

28
no-OH
X bCH-CHz-CHy-OH +
Hy
3 moles

Examples
as - mer/out · on

m
Be n
↳
↳it 202
m

Don
F
(d) -
130+ Rig expansion
HBO TON
X

Bats/MD
 in Carbocation
Ring Empansion

cost(207)
T Mydride
->

↳ shift
Ito much
angle straint
not
possible]
rodwide si e

jet ↑
sp2(,20"
I too much angle strain
not
-

possible I

Rig
-

Ring
it red
strain 6.3 97
at/ real/ ke
not not mot
- a ne

I
I
5
t
·
2-3 Bond break
2 3
+

2 2
⑳

7 I
-> 4
I · ·
1.3 bond Join.
3 3 54
·
charge of goes

3
3

I I 3
- I
⑧ I
- 2 2
2 -

I 5 &13
I
C13

·
I
4 - ->
2
I
3
I

-f ->
3
54
 From halides.
↳
alkyl
Polar
R-x +
aq.
KOH >
ROH + HX.
aprotic solvent

SN mechanism]
-

[It
follows
The reaction
follows new
this -> 3)2

C) from Carbonyl compounds [my Reduction]

The Reducing agentsused are -> M2/Pz, pd, No

->
NaH4
->
LiA4

Aldehydes and ketones by wing

·
are reduced all thethree

reducing agents.

Achyde Hprimanyalohot refore ye are

·
increas

i
H

m
⑳

i
in or
H -

20
=

t H -
H 7 H -2-OH
Nat4
1. Alcohol
O
H
I
M or
0H
H
R-4
0 + -
H > -

Littl
H

e=
-

Bien-on IsR that

I
Mar
R -
I H -
H ↳
NaH4

·
Carboxylic acids are reduced to alcohol
by using
a strong Reducing agentLAHq.
--.O.H
H 1 H2
R -
R-CH2-OH 0
, Hy
-
+

Litt
 itis
SinceLetpensive reagent, we
are preparing
·

Barically acids are reduced alcohols

to
by conventing
in
them
Lo ester
followed by reduction wing hydrogen presence
of talpt.

pro-Reno
0

-ok + H-o-R' Estenfication,

H2/Pt
/

R-CH2-OH + R'-OH

(d) From Grignard Reagent.

6 3dt
c- (Addet)
"
12
-

0 R Mg x 0
my x
=

+ -
- - -

-
↳ -

Shefirststepon
OH-H
Reachine
·

in

+ Mag (ox) x
·
On
alcohol.
hydrolysis, adduct
the
gives
Yx-
Y H R
I
I
H -
C 0 =

R= 0
=

R2 =
0

R-Mg -X
1, v
R-Mg-X 2
R-MgX

H R
H

1 c-0- MgX c- 0 4 c
R 0
M x
- -

Mg-
-
- -

x
-
-

i E R
↓20 ↓ 20 ↓ 120
H
k-2-on+magon)
H
I
R
-c -on+ Mglon) X R - > -OH+
Mylon) x
x

↑
19 R 127 39
in
 2) Industrial method of preparation:
H20
22 H22 01 > GM120b + GH2Ob
Investase

↳
Zymene
2245OH +
2L02

As alipheticamines:
From

not
R- +
troy RoH+Ng+He

Method of Preparation of Phenol.

(a) From Haloaques [Dow's process]:

el Nat

-
I
I
NaOH
623k
-I, rice, trace
300 atm

From
(b) Benzene sulphoric acid:

thatus,
SO3H OH

1 I
orum
7 1, moon, In
come.
H2SO4

↳ From Benzene diazonium salt:

itc-troms +
NH2

- Naroy they
I 00-50C Na+ nd
 (d From cumere:

Isopropyl benzene

Cumene is oxidised in the presence of air to cumene hydroperoxide. It is converted to

phenol and acetone by treating it with dilute acid. Acetone, a by-product of this reaction,
is also obtained in large quantities by this method.

My C
f

Cz-e: H CHy-0-0-H
ot -,eng-- e
00 I O

- I
02
7 - ,

sumene hydroperoxide

Chemical Properties of Alcohol:

·
Alcohol actsas bornnucleophile aid electrophile.
alcohol act devage
when
nucleophile of bone occurs.
·
as
·
when alcohol act as electrophile 1-0 bond derage occurs.

Alshot actsas nucleophile>

I +L

R-8-H+ Ye > R -

--
0-1 >
Bo-kat
This proves the Acidic native
of Alcohol

Alcohol adi as
dectrophile> [Protonation is be
to done]

&o

>R-ON2
↓ A
R-0-Hd
+ H

-
-I
Nu R-0H2 > RuNut 40
X
· Reaction involving bond
out derage:

a) Aidingof alcohol and Phenol:

·
Reaction withmetals.

2
CHg-OH + 2Na <
Ha+ 2Cg-oNat
6 R-OH + 2At >2(50)A + 3H2

ON O-Nat

2 =
1
+ 2Na >2 =
1
+

12

·
Reaction with-metal hyponide:
RONat +H2O
R-OH + NaOH >

the above reaction is

possible if R= cty CHOH is
*
because
a
strong acid than H20.

Other Alcohols does not this reaction

give mater by because
He is a stronger acid than othic alcohols.

Acidic strengthof Alcohols. 13

C3 -
-
CHy0H CHy CHG-OH &H-OH C-OH
:
·
7

23
60 10 20 30

Increase in the +I
effect1 4 increases thenegative
group
chasse demilyover oxygen then
the release
of hydrogen
is
difficult. They inacidic character decreases.

ButCHyOH is more acidic than

water

Acidic strengthof Phenols.

ON o

1 - 11 + Nat
Phenonide ion
 ·
The Phenoxide ion is much more stable due to theresonance.
Phenol is more
The acidic than alcohols.

the phenonide in win more stable

mithoraning
be
if Hudson
·

group is attached to phenol in ortho and

the
para position.

0 0
O
O -
u I
↳
E
-

-I -
I I I I / -
a
7 -

(b) Esterification Reaction.

Alcohol and Phenol reachwith-carbonylic acid and acid derivatives

-

acid chloride and acid any side ↳ give ester

⑧ O
nt
R - 0H R R-0- R
-
⑧ -
+ H- 0 -

↳2504 + H20
0 0

. R-0-n+c-4-R dine R-C-0-R -nee

i

Mechanism.

~ -
0-A 0 -4
nt O-H
R -oh -R-C-O-H,
I
I ROH
R c-
R-E8
So -
-
-

o -
n
I

R -
V
+
In-shift
O 0 H
+
-

4-0 R--oR R-cotz

/
R - -
R =

↓- B
The reaction with carboxylic acid is carried out in the presence of a small amount of concentrated
sulphuric acid. The reaction is reversible, and therefore, water is removed as soon as it is formed.
The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to
neutralise HCl which is formed during the reaction. It shifts the equilibrium to the right hand side. ↑

b group in alcohols or phenols is known as acetylation. Acetylation

The introduction of acetyl (CH3CO)
of of alcohol produces ester and salicylic acid produces aspirin. Both takes place in presence of
sulphuric acid

⑧
name
o ⑧
-
O
"

R-C-On +
O

R-Y-O-R

Cool O
COOH O O el
no I R O
o -c

-0
-

8
-

H+ R -
-o - R
-
X -I I R-
11

c-OH

Aspirine
salicylic acid -

2-actoxybenzoic acid

⑧ Reaction involving 2-0 bond derage:

as Reaction with-Hydrogen halides.

is For MCL: 1 Reagent used
any Enc]
Mialive Reagent.
of
tee and
away Enck -> Lucas

This process is called - >

GROOVE'S PROCESS

CHy-CHz-OH t He awhy, CHICH-C +

H20
Enc
(10)
anhy
led 1
CHy-CH-cy+
on
znee"
CH-4-C+
129
 CHeb
--- on that
any Inc is
not
X
cres-2 10
+

CH rege
CH3
his For HBer: [Reagentused H2SO4 I

Nar +
H-HSO4 ->
NaNSO4 +HBr

[Hpe is produced in sili

CHCH-OH + HB 3
CHBC-Br+H20

(s For HI: [Reagentused H3P04]

&I H-H2P04-> kHPOp+HI
+

CHy-CH2-OH + HI <
CH5C-I+H0

(b) action of 'x 2

By the PXs and PX5: =

X
- R- of
R-OH I P X >
H3P0y + 3R
-
X

R-OH X

SO, 3ROH + PYB > 3R-X +

H3POg

- R -
0 -

H
Ch SRC+ POC + UCL

e - -e
--

a cl

So, ROH +PC5 R-C POL

+ + Hect
 (C) the action Red P and Xe: [X=Br,
By of I

I P4 6P2
+

>4PBUs
3R-OH +
PBry->3Rr+ HyPOs
7 P4 +

6Iz >44I3

3R-OH +
PI3 > 3R -I +

H3PO

(d) By action
the
of thionyl chloride

this is the
way for thepreparation
best
of alkye chloride
as the
by-productformed escapes in the form of gases.

R H
0-
-

u
11

a
>R-a+ son"+Ha
-

S -

Best
yield

⑧ Reaction involving 1-H and 0-H bond derage.

x Xchydration Reaction:

It is theremoval of 10 molecules in
presence of Mason, H3PO4 or

CatalystAldly Alumina which

or acti as
dehydrating agent

Mechanism:

CHy-CHL--H+
-Isop-eg-jo+ -

H20
aso
I

H2SO4
on], C
-
+
CH2=CH2

[larbocation
 cone. H2SO4
CHz-CH2-OH y CH=CH2 +H20
443k

IP alcohol]
413 80% H3PO4
CH5-CH=CHy+HO
Mg-c-on
>
440R

[e"alcott

as-ce+H0
CH3
I 20% H3PO4
-
CH-4- OH
350R

CH
[3o alcohot]

Questions.
I H2SO4
& it
X
-he
dre
+

H 7 V

A
L
-

[Major Pdt]
TOH
I com.
12604> Protonation -
Ring expansion
7

-ne
E ~ne In
↑

H X 7
/
I I

3 X

-----
2
E S
I
f
&
↑
2
tr
↳
- X -

X X 7
f

X
- - -

[MajorPat]
 (b) Oxidation Reaction:
[O] [O]
R-CH-0-H Y R CH 0 > R-COOn
=
-

oxidizing
in agent

· This reaction is also called dehydrogenation reaction as it

involves theremoval of 12.

strong oxidising agents:

Jone's reagent[icCros]

I
- acid
This conventi alcohol is
-
KeCrcO 7 /nt
->
NacCr207/ He

Milo
oxidising agent:

3
this corrects alcohol to
alschy de
->
cos (anhybous)
-> PC -
[Pyridinium chlorochromate]
↓

N ⑲
H
0-c-e

·
R-CH2-OH
[O]
R-CHO
[O]
K2C207/n+3
RT-on
K2C207/+
(Palcohol)
<rob [anhydous], R-CHO

or, PCC
[Preffered for the conversion
of alcohol to alochyos]

· R-cob -on -R -
k0
R
=

anhy
(2" alcohol)
>[Preffered for theconversion
toketone
of Zalarhat
-

Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as strong
oxidising agents (KMnO4) and elevated temperatures, cleavage of various C-C bonds takes place and
a carboxylic acids containing lesser number of carbon atoms is formed.
·
Mb
cz-s- on come. HNS

KMO4
or
x
enco 4[0]
- Cha-cy+costco
1 -

che*-e e-elite
enolization S 40s
CHTOH
>
I +
C02 42 0
y &1 L
O
H

·
Dehydration Ran also takes
place in presence of
Cu 573R

a
R-CH2-OH > R
- CH 0 =

573
R R
a
C
I

R-CH-OH 573
>R -

0
=

R R
I

R -

P
-
OH
a
> R -
c ca=
-
H20
573
CH-H

Distinguish between I, and 30 alcohol: [Lucas Test-]

1" alcohol
anhy
CHy-CHz-OH t He X CHICH-C H20
+

Enc
(10) No
turbidity.
2o alcohol
anhy

CHG-4-cyte
He
CH-4-C+
↳
Encez

129
Turbidityafter 5 mins.
3 alcohol
CH3 CH3

cra-c-oH + Ha
any Inc is
not
X
cres-2 10
+

CH rege
CH3
Instant turbidity
 Chemical Properties of Phenol.

2) Acidic nature Phenot:

of
OH 0 Nat
I I
2
0
I INA >2 0 -
H2

of ①Nat
I I

0 + NaOH x0 +
H20

(b) Reaction with Zine:

On
I

0 I Zu 7 0 + EnO

↳ will-Aid
Reaction and acid derivative:

Phenol reachwithCarbonylic acid and acid derivatives acid chloride

and acid anhydride I give ester

⑧ O
nt
Ph--OH n-o-R Pe-0- R'
~
⑧ +
H20
+

↳2504
0 0
Pysidine
G-C-R Ph-c-0-R -nee
"
. Ph-0-H+

⑧
·name
o
⑧
O

-
O

Ph---on +
O

R-Y-o-R

0 0
Pysidine
--Ph
I1
. Ph-0-H+ c -
Ph-C-0-Ph - He

IPhenys benzoate

Scholten Baumann Reaction

 (
Electrophilic substitution Reaction:

In phenols, the reactions that take place on the aromatic ring are electrophilic substitution reactions.
The –OH group attached to the benzene ring activates it towards electrophilic substitution. Also, it
directs the incoming group to ortho and para positions in the ring as these positions become electron
rich due to the resonance effect caused by –OH group.

is nitration:

OH OH OH
I 11
-Nor
0 - dil. HNOD > 0 + 0

use
The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam volatile
due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to intermolecular
hydrogen bonding which causes the association of molecules.
0-1......
1

0
-
N0
=

Intramolecular
H-Bonding

0 0
21 21

OH- -

N-0---..- HO- -
N -
0

Intermolecular
H-Bonding.
OH OH
↓ +> come. HNOD >
nor-
I

0
-Nor Pixinacid
->
2,4,6-Trinitrophenol
nor
The product is commonly known as picric acid. The yield of the reaction product is poor. picric acid
is prepared by treating phenol first with concentrated sulphuric acid which converts it to phenol-2,4-
disulphonic acid, and then with concentrated nitric acid to get 2,4,6-trinitrophenol.
 OH OH OH

↓
I sObH I
- come. nor- -Nor
+> come. H2SO4 > 0 7 0
HNOD
I
SbH Desulphonation nor
(i) sulphonation:
OH OH OH
I I
I 50zH
/
0 0
+> come. H2SO4 > 0 t

I
SbH

(i) Bromination:

OH OH OH
I
Biz/RO I Rat I

0 - 0 I 0
Polas Protic
solvent
OH ise
Be I
De
Bit U2 -
-

7 0
solvent-
polar aprotic I
Re

2,4,6-Tribromophenol

Les Kotbe's Reaction:

Sodium pheroride undergoes electrophilic substitution reaction

withweak electrophile my to give Salicylic acid s

OH O Nat OH
I I I won
NaOH
>
we ~
0 0 > 0
He

2-Hydonybeneric acid

$ Rmel-Tiemann Reaction:

OH OH
I -HO
I BNaOH
+

+Cay 7
0 2420
+
+

3NaCl
 Mechanism:
⑧
el u
V
OH
a -
e C H NaOH c. TC is
el
good leaving group.
-

I > a

el
e
↓

D
2
[Sichlorocarbene]
I

· Ch M

is
O 4S
I V
-- e
12 Ch

-I
E - - I
I -
a

On On On Ch
OH
2H 0 I CH 2 NaOH I CH
I =

nt el
[ -
OH -
-
-
-

H20

Phenol
Test
for

(a) FeCty Test ->

6 PH-ON + fedz >F(ph)s] + eech

nene
phenonide ferrate (III)
violetcoloured

(b) Azo-dye test >

NC+ H OH
-

Hec

-
N =
N -

0 -OH

P-hydonyazobenzene
orange dec
Physical Properties of Alcohol and Phanots:

The Alcohols and Phenol increase winthe

increase in
B.PA
·

The C-ators due to the increase in vanoerwalls

no.
o free

In hedeceases
alcohols thewearinare
with
·
Manches

surface area

·
Alcohol and Phenol have high B.D in camparison to other

organic compounds due to intermolecular H-Bonding

- -

·
Alcohols and phenol are soluble in water due to this formation
of it-Bonding.