Alcohols and Phenols : -

→
when
hydrogen
\,

of aliphatic
primary (
a or
Tertiary (5)
aromatic hydrocarbons is replaced by C- OH] group
t)
secondary (2)
then
called
the compounds
alcohols and
which are
phenols
obtained are

CHS Ctf -
-
OH Ctf -

Ctf
-
CH CH
}
- É%H
} }
tote
.

OH OH
R H
-
> R -
OH
Alcohol Allylic Alcohols
Aliphatic Hydrocarbons
•

In this type of alcohols OH

9804 .
-

OH is attached the to Sps hybridise d carbon which

>
¥-0M itself attached to a double bonded carbon atom
Aromatic hydrocarbons Phenol
Ctg = CH -

CHA -
OH → Prob -
2- en -
1-01
%• Also called Hydroxy derivatives of Hydrocarbons
Benzylic Alcohols
•
.

In this type of alcohol the OH

Classification of Alcohol and Phenols
-

group is attached to the Sps hybridized carbon

attached
•
On the basis of no -
of -
OH
groups -
which itself to a benzene ring .

OH
¥441 alcohol
-

t
.
↓ ↓ →
Benzylic .

Mono hydric Dihydric Tri or bharat panchal 92

polyhydric •
Vinyl ic Alcohol :
In this type of alcohols OH
9804
-

OH CH OH
City CY
OH
is
-

attached to double bonded carbon atom

-

, a
, .

08
t.tk - OH
GH
- OH
C. Ha = CH -
OH → Vinylic Alcohol
or CH, -
OH

[H #
%
OH

4%011
NOMENCLATURE :

YE OH
-

"
EH} 3,3 -
Dimethyl Benton -2-01
OH OH (
Hz G GH CH
- - -

}
OH
↳ Hs
G@BGG-oBharatPanchal-ChemistryGuruji2.o
 •
structure of Alcohol and Phenol group :
142 PM 109
.

"
µ
c
&¥µ"Pm Ec
"

108.9
.

↳
136 pm
No "
The C- 0 bond length in bhenol is 136 pm which
is less than alcohol due to

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

acquire partial double bond character -

Iii ) In phenol oxygen atom is attached to

spa hybridise d carbon .

Preparation of Alcohols :
" the sing
B-
{ ,=§jcH
OH Draw
From Alkenes :( BY Hydration of Alkene )
•
-

,
Hex -1
•

µ
-
en -3-01
"+
( O H
CH CH H2 + H pH
-

3- Bromo -4 methyl
- -
- _

]
CH
-

cty.CH - CH -
CH -
CH -_
"
, ,
CH CH]
,
CH ]
bent -3
-

1-01
-

-
en -
"
OH
bharat panchala Poop an -2-01
in
-

when alkene react with water the

NOMENCLATURE of acid catalysed then alcohol is formed
presence
.

OF unsymmetrical alkene when water

On ,

PHENOL is added then product is formed

molecule ,

according to Markovnikov 's Rule .

Mechanism :
H2O + H+ → Hz0+
I
step -
 > e- of + H¥É±H ÷ -

↑ - E: + tea :O.
Aldehyde
R CHO
-

+ H2 R -

CHA -
OH
2. alcohol

R R
step GH
F- at
2 : R R TH
G
- -

2. alcohol

:c ¥
-
-

÷
• .

,
% :O
OH
+
-

. -
.
From the reduction of carboxylic acid
.

•
& ester
Step 3 :
µ H H It
R f OH +4Gt] i R CH OH -1110
& É -4-4--1%0?
- -

& ii. + Ha :&

-

,
-

→ ,

Alcohol
0
Carboxylic Acid
-
- -
-

+ A "A ""
+R OH
R CH, OH
'

'

4TH]
-

Oxidation R C OR > -

By
+
-

Hydro b oration
-

• - : "
Alcohol
8 ester

3kHz CH -_
Ctf ) +
&B2H , > CH] CHA CH
} B
-

Grignard Reagent when

-

From
-

, • :

grignard reagent react with

OH +311202
-

{ aldehyde and ketone then alcohol is formed

3kHz -
(
Ha (11-04)
-
, .

BCOH) } bharat panchal 92 =c=%+ñ-Ñig-✗ >

[ orig × ]
%
+ -
-

when alkene react with diborane ( Batts ) ,

then trial kid Adduct
borane is
formed which gives alcohol by the oxidation
> OH + MGCOH)✗
gig
-
'
of Hack in the presence of sodium hydroxide .
yo
From carbonyl compound : ✗ # H CH OH -

-1mg !%
Mg
-

=otR
H-GH-o.mg
# →
-

k
,
•
By the reduction of aldehyde and ketones formaldehyde 1. alcohol

R-fgte-o.mg#Yr-cH-0H+Mg1ouk-2oalcohol
Aldehydes and
ketones reduced the
corresponding %c=o+R-Mg✗
→
are to alcohols *

by hydrogen in the presence of reagent like

Pt , Pd , Ni Li AIHA NABHA ele

3° alcohol
.
, ,
# Ketones give r
{ In the presence of Pt/Pd take Ha & rest

R%=o R-mgx-i.gs?i-omgxH--Hg-c-0H-iMg::..
we

of these take QH
} +

Go@GG-GBharatPaneha1-ChemistryGuruji2.o 3. alcohol
 ofromcumenf.IN
l

Preparation of Phenol
is oxidised
this method cymene
in the presence of air then cumene hydroperoxide
from Haloarenes obtained Now it react with acid
is . dilute ,

Chlorobenzene is fused with NaOH at

and acetone
623K and 300 atm Phenol is obtained gives phenol
by
.

pressure .

Ftl}
acidification of sodium phenoxide "
1-i o o it
OH
f- Nat ,0H
- - -

]
%
il "+
§;]
ask
#
, , + CH C CH}

Fj
,
- -

I }
+ NaOH Foam "
◦
cymene cymene hydro Phenol Acetone
peroxide
•
from Benzene Sulbhonic acid :
Benzene is sulphonate d
•

Physical Properties
benzene sulphuric acid
Boiling Point
with oleum and so formed is :

converted to sodium phenoxide on heating with the b.pt of alcohols and phenols increase
with
molten sodium hydroxide increase in no .

of carbon atoms ( increase in Van

der Waals forces )
EI
POSH
" " " Point of is ethanol
¥
butanol than

%:#
more
"
e.
g Boiling
.

>
i increase
→ In isomeric alcohol , the B. Pt decreases with
in
• from Diazonium salts : branching i. e B.pt follows the order
diazonium is formed
.

A salt 1° alcohol > 2° alcohol > 3° alcohol

by treating aromatic i amine with nitrous acid
an
[ Because Van der Waal forces
of decrease in
( Manoa 1- HU ) at 273K -278K Diazonium salts
with decrease in surface area ]
.

are hydrolysed to phenols by with

warming
with dilute acids → The OH
group in Alcohols and phenols is involved
water by treating
-

or .

in intermolecular Hydrogen Bonding

1^1112 1%+6
'

Nano , 11,0 bharat panchal 92

, /
2 -1116
" + Na
pyo p
ri
H H H
pyo
> -

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

+ Ha warm
-

R
Aniline Benzene diazonium phenol .

Chloride " "

 b.) Acidity of Alcohol
Solubility
-

:
acidic nature alcohol is due
The of
→
solubility of alcohols and phenols in water to the bolar nature OH bond
of
-
.

is due their Bonds with

to
ability to form Hydrogen alcohol
water molecules .
*µ In an f- CH g
,
e-0
releasing group -

GH 5) increase
the eo density on oxygen atom and decrease the polarity
→ The solubility decreases with increase in size
of of OH bond Due to this the acidic strength of alcohol
-
.

alkyl / aryl ( hydrophobic ) groups also decreases

.

H
Therefore order of acidity of different
H O
Q the
%
H
- - - -

H
-
- -
- - - -
- -

H R te alcohol is as _ ..

pm chemical Properties of Alcohols :

R * Ctf -
OH >
R"
*
CH -

OH > 2¥
R
# OH

3°
1° 2°
1. Rxn in which cleavage of -
0÷H bond takes place
2 Ran in 9. why alcohols are weak acid than cornball to water ?
which cleavage of -
( ÷ OH bond takes place
AE In alcohol
,
alkoxide ion is
formed after removing H+
# Rxn in which
cleavage of - O -
H bond takes place ion and in water hydroxide ion is formed after removing Htion .

But alkoxide ion is less stable than compare

10 alcohol > 2° Alcohol > 3° alcohol
to OH ion due to the of more eo density
-

presence
it Acidic Nature of Alcohol and Phenol
on oxygen atom Therefore alcohol act .

,
as weak acid than
a) Rxn with Metal compare to water
Alcohols and phenols react with active
.

0÷H H+
-

R → R O +
metals such
-

and aluminium
-

as sodium , potassium to
Alkoxide ion ( less stable )
yield alkoxide / then oxides and
corresponding hydrogen
Acidity
.

c) of Phenol :
2 R O -
-

H +2 Na → 2 R O - - Na + H
, phenol is more acidic in nature
sodium alkoxide than compare to alcohol
pH in a
.

bharat panchal 92
Reason
,
:
ionisation alcohol phenol
k¥ of
+2 Na → 2 The and
1- Ha takes place as -

Phenol sodium bhen oxide + It -1

R -
OH
'
R -

,
OH
,0Na PH
Alkoxide ion

¥1 + NaOH →
¥1
sodium phenoxide
+ Hao
Fit ÷ É + "
+

]
G@BGG-oBharatPanchal-ChemistryGuruji2.o
Due to the
higher electronegativity of Sb hybridise d
 carbon of phenol to which -
OH is attached , eo density Esterification of Alcohol -

decreases on oxygen This increase the polarity of

Rxn with carboxylic acid
.

result in
-

OH bond and an increase in ionisation of

O R -1110
§
HO R R
R f -1011
- -

phenols that +
-

that alcohols
- -

of .
,

alkoxide ion is formed and in

A aft
In alcohol Alcohol .

Phenol
,

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

Rxn with Acid Chloride

stable due
-

more to resonance than compare

•

to alkoxide ion P" "dine

OR -1116
§
a H O R R
.

ff
+
-

>
R
-
-
-
-

is
-

Therefore phenol more acidic than alcohol .

following observation Rxn with Acid Anhydride

g. Explain
the -
•
-

+ R C OH
% _
OR
-

b- nitro phenols acidic than phenol R

§
-

o and are more R OH + R

-

8
. - -
- -

Au No, being an electron withdrawing grouts when R

§
. -

present at ortho and bara -

positions withdraws
co density from benzene
sing thereby decreasing the •
Esterification of Phenol -

CH]
o
make the release
- -

co density of OH bond and thus "

of proton easier .

É +
CH, -

§
-

ce ¥1phenyl acetate (esler)+116

o==niI-
phenol
H o Ñ → Ht +
%
'%

1¥
"
-

CH,
%:* § acid
µ++Éy=ñ%
H OH
-

p niko phenol is " 1- CH,

- -

0
-

-
+

ni as §
.

> Phenol Acetic

\
O_0
nitrophenol Reaction in which Place
0 -

cleavage 7 c- OH bond takes :

this tube of reaction , alcohol behave electrophile

group intensifies
Also In as a
,
the -
NO
,
the are charge of phenoxide
ion and thus , stabilise it and hence increase its acidic •
Rxn with Hydrogen Halide

strength
Éj
as 2h42
"

"
^ R OH + HCl 7 R Ut Hao
- -

s
-

<
IN 02 mixture of HU +2nA
,
→ Lucas Reagent
para nibobhenol more acidic
"%
Hence ortho and are CH CH CH Cl
CH OH tea
- -

g
e- + ,
z ,
- -

} ,
than phenol .
Lucas Test :
Mechanism of Dehydration of Ethanol :

alcohol 3° alcohol
Dehydration of ethanol in the presence
'

2 alcohol
'

1
of conc tyson
fH3 involve the following steps :
CH] -
CH -
OH CH] -
{F- OH CH
}
-

f -

OH
,

CH step -1 Protonation of alcohol

¥ teE- %%
,
HU HU

+2mHz
HU
É É ÷+i+ fast
+
2nd, + + -

H
\,

-1%3-6
- -

2h42
-

v
n
CH , CH, -
-

Cl CH eats te te
,
"% Protonated alcohol
+ Hao
{ ,- 4
-

+ tho µ
+ Hao
( ethyl Oxonian ion )
Turbidity step -2 Formation of carbocation
Turbidity Turbidity H H
appears after "

! - % f. +110
appears after appears is a- *

heating
-

5min a- a
immediately
_

te
.

Dehydration elimination of Proton

water molecule alcohol step -3
Removing of from
Ctu
H H
is called dehydration of alcohol It is an elimination -

'
+
= + ut
a- c
reaction in which cone Hasan , Phosphorous Penta oxide .

Ethene
h H
CIOs) , Alumina ( Ako] ) is used for dehydration and
.

alkene is formed product Oxidation

oxidation of alcohol involve the formation of
-

as .

bond with cleavage of an

'
O H
'
bond
x > c- Cf -1110 carbon Oxygen
-

d- d-
-

'
bond
-

and
'

Hasoy C H - .

i bharat panchal 92
H÷& YEO TH ,
→
-
o H

The order of reactivity of different alcohols * This process is also known as dehydrogenation
1° alcohol
3° alcohol > 20 alcohol > .

Primary Alcohol It is oxidised into aldehyde which is

further oxidised into an acid .

CHO CH, COOH

GaB@0GBharatPanehal-ChemistryGuruji2.o ( Hy CH Ctg
-

-
-
OH -

, -

↳° Aldehyde Acid .
 Secondary Alcohol •
Rxn With Zinc Powder -

It is oxidised into ketone which is

further oxidised into acid
*
+ 2h
! + 2h0
% to] Kdr°Hhj ◦
> CH
=
-
OH + Phenol Benzene
CH
-

%° CH
] 36] •
Rxn with Phosphorous Penta chloride CPUs )
,

<
got
CH, - COOH 1- HCOOH + Pus > + Poll, + tell
Tertiary Alcohol
oxidised in ordinary
It is not
Rxn due to benzene of phenol
condition in the presence of
but
strong oxidising ring
a mixture of is formed Resonance in phenol
agent , carboxylic acid .

Dehydrogenation :

↳ CH CHO +
( H2
-

OH >
CH,
Hy ]
-
-

(B) CH - OH ÷ , MY
'
-0 + H,

CH CH
, ]
'

In
of }
.

case

ICH ]

ay ,
¥2 alcohol, delve
dration takes
-

As a result of resonance ,
electrophilic substitution
% f OH position
-

Rxn takes place at ortho and para

-
-

{tg Place
.

CH
] Nitration OH

"°
Rxn due to -
OH group of phenol dit HNO
-

},
- -
b- nitro
¥,
+
278 -288k phenol
bharat panchal 92 in, , ,
•
Rxh with Ammonia phenol 0 -
Nilrobhenol

%%qo
PH "° NO,
PH " no HNO ]

+ NH} # , 0 2,4
,
6- Trinitrophenol
Acid )
2h42 "

Now
( Picric

Aniline
GeB@GGBharatPanchal-ChemistryGuruji2.o GoB@0GBharatPanehal-ChemistryGuruji2.o
Notch The ortho and basra isomers can
Nibobhenol is
be
steam
separated
volatile
Halogenation
when phenol react with bromine in the
by steam distillation .
o
-

presence Cay at
low tents then
due to intramolecular H -

Bonding ,
while b- nitro phenol of Csa , CHU
,
or ,

is less volatile to ortho and bara bromo phenol is formed

due intermolecular H
Bonding which
.
-

OH

Éʳ+☐
causes the association of molecules 1011
" + Br . →
ii.
Ho -
E- No . . ..
Ho -

TIN phenol 0 -
Bromo ,

b- Bromo
. .

phenol
0 - Nitro phenol b- Nibobhenol OH 011 phenol

( intramolecular H -

Bonding ) ( intermolecular H -

Bonding ) [¥+3Bn → BY - Br
24,6 -
Tri bromo
@ %)
Kolbe 's Reaction 1B , phenol .

Phenoxide ion is more reactive than

phenol towards electrophilic sub reaction Therefore Oxidation :

of phenol in the presence

.

of air with
.

oxidation
when phenoxide ion react with co
,
, then salicylic
chromic acid ( Madriz -11150*7 form benzoquinone
acid is formed as a product This .
reaction is called
Kolbe 's Reaction
OH PNA
it COL
- COOH +0,
N%CK°7
> Benzo

-4
NaOH
,
ii ) Ht
> Lot 11504
no quinone
Sod Phenoxide 2- Hydroxy Benzoic
Phenol bharat panchal 92
Ethers ( R
.

acid -
O R -

)
( salicylic Acid ) ether is
Reimer -
Tiemann Rxn • The general formula of Cn Han -120
when phenol react with ◦
In ether two alkyl grouts are attached with the both
chloroform in the presence
of sodium hydroxide side
then salicyl aldehyde is formed as a product .
of oxygen atom R O
- -

This is called Reimer -

Tiemann Rxn .
o Ether is also known as Anhydride of Alcohol . .

Na ima
R → R O R
go area
jcH0 R Hao
CHU NaOH NaOH OH + HO +

[
-

+
-
-
-

} ,
,
Anhydride of
,
Ether ( Alcohol )
Types of Ethers
Enter
a

mediate
i.
011
'

simple ethers mixed Ethers

_

"" OH
1¥
H -

CH
f
CH
]
-
O -

} # 0 -5¥ 4115 - O -

CH
, , ! -
O -
CH
]
hyde
Salicylate ,
Common & IUPAC Name of Ethers Mechanism
The formation of ether is SNI involving the

attack of alcohol molecule on a Protonated alcohol .

(f)
'

CH
]
-

CH -
H+ → CH -

CH -
H
, } ,

( iil CH CH
Oi Ctf - TO
:
+ CH] -

CH} CH CH
-

, , →
CHA
-
- - -

'
, ,
H
H
+ H2O
( Iii ] CH] -

city -¥ -

CHI -
CH
]
→
CH (
] Hy -
O -

CHIEH] + Ht
H

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

takes place by SNL mechanism

'
R X -
+ R' -
o -
Na → R -

¥ -
R + Max .

structure of Ethers : CH
( c- the ) fth
•

, ,
The bond angle btw C NaBr
f- &
CH +
CH Na -1
1- CH Bo → CH
-
- - -
-

] ] ,
is
-

grouts which
'
111 due to repulsion between alkyl ,
,

CH}
{H]
are attached to oxygen atom
141PM
a. In case
of 2
'
and 3° alkyl halides , elimination completes
CH }
4¥ CH ] over substitution If a 3° alkyl halide is used .

an
111°
alkene is the only reaction product and no ether is too med
Preparation of Ethers

By dehydration of alcohol
pH ]

-101011
•

CH -
C -
Br + Nat _ - CH
]
→ CH
]
-
G- CH
,
+ Na Br

Has 04 3
I { H]
CH CH, OH
, CH2=CH2
, 443k 4^3 bharat panchal 92 2- Methyl propane
Has 04 phenols are also converted to ethers by this method
> GHS
-
-
O -

GH g- .

413k "" "

" +
"
+ ctg-ctg.BR a- I + Na Br

GBAGBO Bharat Panchal -

Chemistry Guruji 2.0 Ethoxy benzene

sod Phenoxide
.
Physical Properties of Ethers Note
when one
of the alkyl grouts is a tertiary group ,

Ipi methyl ether and diethyl ether and other

are
gaseous
•

in
the halide ion is formed is a tertiary halide
ethers are liquid nature .

•
7 Ethers are
lighter than water i. e density is less FH] fH]
CH CH] 1- HI CHI OH -1 CH ] C
water f O I
- -

than
. - -
-
-

}
volatile in nature thy
•
) Ethers are highly .

CH
]
•
) solubility ethers are partially soluble in water
•
Electrophilic Substitution Reaction
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
.

OR group is ortho and bara directing .

Therefore
Chemical Properties substitution takes place ortho
electrophilic on
it Hydrolysis and para position of benzene ring .

↳ 0s -
O -

↳ He + Hao , & ↳ Hs OH -
bharat panchal 92
Tsonga
'
✗
•
Halogenation
with PCH] PCH}
i; Rxn Halogen Acids : PCH] Br
Bra É
+
+
HI ? H Br > HU 7 Hf acid '
bharat panchal 92 0 -
Bromo Br
Anisole
Anisole b- Bromo Anisole
# Reaction with HI :
react with HI in
when ether (major )
hot and cold medium ,
then different product is formed r• Nitration
H OCH ]
PCH]
-
I

GH g- IF 2 Calls I 1-

É%
↳ Hs O Hao
-

""
-
-

I -
H +
Cone Has 04
ÑO2
.

H I ¥ ↳ Hs -
-
OH + ↳ Hs .
-

I 0 - Nitro

↳ Hs -0 GHG + Anisole p Nitro anisole

-

ethyl alcohol ethyl iodide

GBAGBO Bharat Panchal -

Chemistry Guruji 2.0

ra Frieda craft Reaction SOME COMMERCIALLY IMPORTANT ALCOHOLS
•

Alkylation OCH ]
1.Methanol ,
CH} OH ↳ also known as wood stirk

É"ʰ
preparation
PCH ]
+ cusa
É +
, By catalytic hydrogenation of carbon mono oxide at
high
( S2 '
CH } pressure and temp .
in the presence of 2h0 -

ergo, catalyst
2- Methoxy 2h0 -0203
toluene ( minor )
4- Methoxy CO
-12112 > Ctg OH
toluene
.

200-300 atm
•

Acylation cmajor) 573-67319

PCH] CH
] Properties
'

+ CH Coo
,
¥ -
coats +
•
it is a colourless liquid and
highly poisonous
All] •
It is completely soluble in water .

'
COCH]
2- Methoxy Uses
4- Methoxy
ace to the none - It is used as a solvent for paints .

acetobhenone It is used for the manufacture of formaldehyde

-

It is used as an antifreeze for automobile radiators

-

Denaturation Of Alcohol
.

commercial alcohol is
It is used for denaturing ethyl alcohol
-

The .

made unfit for drinking by mixing

it with some
2. Ethanol ( ↳ Hs OH ) -

copper sulphate and

methyl alcohol .

Power Alcohol
Ethanol is mainly obtained commercially by fermentation
of
-

Absolute alcohol mixed with petrol sugar .

Invertase
(
(
roughly in the seatio 20 : 80 ) is used in internal 421122011 + H2O > 6111206 + ( 6141206

combustion engines .
this is known as tower alcohol
24 Mase
mixing is done in presence 1% benzene ↳ 1112 06 > 2GHs- OH +2102
of or 1% ether .

Ethanol
ALCOHOL ME TRY - Properties
The determination of the percentage of Ethanol is a colourless liquid
methanol
alcohol in a liquid ,
especially be alcohol is known The
boiling point of ethanol is higher than .

as alcohol metre USES -

help in
.

To our -
as a solvent in paint industry
-
it is used as an antiseptic in the form of
rectified spirit
Journey you
.

, -
in the preparation of a no of compounds .

can donate such as ether acetic acid, chloroform,

, iodoform ,