Alcohols, Phenols and Ethers

of alcohols

Classification phenols

Basedonnumberof ongwys
CzMsOH 12 011 412 Oh
I 1
oh Oh
OH cry 011
I 1
OH Ch oh
1
OH
l
monohydiric you
1
Oh
1
on
dihydric
trihydric
Based on type of Caton on
group is
attached c

l Cq Oh ch oh I 1C OH
i
f
Primary i secondaylzo tertiary 5

f Kenyon keen dy je
C
I OH
on
allylic io g c
allylic allylic 39
 i
Cheon en on C Oh
1 i
Y c

Berryhill Benzylic I Benudices

D
0H

vinylic
la
uhess IO
symmdnidtuers
R o R type
Gaz O U eh
9

Zethers
R o R type
9 Cy OCzks Canso cars etc

Nomenclature
Compound IUPACName common name

Methanol methylalcohol
Chyon
Clycyczon Propan I ol n propylalcohol
on Propane 2 ol isopropylalcohol
Chs Cy
on

azuzuzenoon Bulan L ol n alcohol

butyl
 Butare a
yl
CtfMath cry sec butylalcohol
on

959 42 oh 2 methylpopan lol isobutylatrohol

ay
say
2 methylpopar 2 ol tert butylalcohol
ay 4 on

cry
cuz Uh Ethane 1,2 diol Ethyleneglycol
I 1
on 0h

propane1,43
Aid Glycerol
Yon Yoning

cyclohexane cyclohexanol
me

2 methylcyclopentanol

On
Phenol
Phenol
on
s
phenol
2 methyl 0 cresol
on

phenol
3 methyl m cresol
on a

4 methylphenol p cresol
Chy
 OH
on Benzene 1,2 did CATECHOL

on

Benzene 1,3 did RESORCINOL

on 0h

It
1 Benzene 1,4 did QUINOL or
011
o hydroquinone
11

On

9300kg Methoxymethane dimethyl ether

CB octbeney 1 methoxypropane methylnpropylether

3 benzene ANISOLE
Methoxy
ANISOLE
O Ching
ethoxybenzene ethyl phenylether
OR
PHENETOLE
in
Cry 043 2 methoxypopane methyl isopropylether
gry

c'kinetyzing 3 phenylisopentylether
Cons o methylbutoxybenzene
y o
uz Ey o
cry 1,2 dimethoxyethane
Me
p the
l ethoxy I 1dimethylcyclohexane
og

structure of functional groups µ

sp Sps
O
Hey 6pm I v o i
WA H
136pm

n f 1oz go Tsp Nsf

H

observations
O
pm
n the c O n
f n iii in Inn bond angle is slightly
n
lessthan regular
tetrahedral angle 1095

due to more
lip lap
repulsion compared to
bp bp reprustran USER
c o bond in phenols are slightly smaller
and c o band in alcohols due to
double bad character o bond
partial of c
in due to resonance
phenols

In ether the c o c bond angles are

 slightly greater than the regular tetrahedral
angle due to steric repusive interaction
between the two
bulky R g

Preparation of
alcohols

from alkenes
b
fha
Markovnikov addition of 120
with
rearrangement
9 cq cµ ons 1 tho on ons
of
Mechanism
slept protonation alkene to form carbocation
of
Ko t t't thot
c n t nie
g
Carbocation
Step attack
of water
on
nucleophilic
H

I e I I En
Steps Deprotonation to form alcohol

I d
gtfo thot
on
g g
 imd on

Markovnikov addition of 120

without rearrangement

Jed Hgcoadz ithos

nc
dg 4on 4n

y.ae

oxidatio Markovnikov
s
Hydroboration
anti addition of 120
without rearrangement

in.gs EI tHzB03

Hydroxylation
dit KMnoy or 0504 I I
c
cf c
I
c
1
Oh on on
syn diols
epoxidation peracid
n
c
cf
L thot
dy I anti diols
 Romcarbonylcompounds
reduction
AO By of aldehydes and ketones

catalysts tf with pt Pd Nig

doesn't reduce OR
NABHA sodium borohydride
doublebonds
esters e or 4Ahh Lithium aluminumhydride
carboxylic
acids 94
amides
et
R Eh 12
r en n
Pd
aldehyde alcohols

OH
R EK 4
r
din ri

ketones alcohols
OH
0 If NaBHg
E
no K uz c H no uz cu

esters
Ximena strong
explosive 2 expensiveRA

LiAtty
RCOOH R CHIH
Hao
commercially and converted into esters first
acids
followed
by catalytic hychogenaka to give
alcohols

R om Hz
R COOH R COOR Razon R 0h
Ht Pt Pd Ni
ester
 other reagents are
copper Chromite AO Cuczou

R COOR Razon R'OH

AO Cuczou
ester

R COOR 4Atty
Razon R 017

Usiyalkylhalides
R aq Kon
x
or
ROM KX
ag NaOH
or moistAgp
Reaction will follow Snl or SNL depending
on R X a nd solvent

fomGrignand Reagents

r rt C Onyx
CIO t R Mgx
R 11201Mt
v
Adduct
C OH 1 Mg X

R
overall reactions

Hero t RMgX t.R atz omgxk RCHzont.mg x

formaldehyde alcohol

Rino t Rmgx R
Cti Onyx RICH out Mg Hx
aldehyde r r
 alcohol
0 R R

R Y r t Rmgx R c Onyx r E out mg H

I 1
ketones r r

alcohol

Exam
ples n
Yc
PhMgBr Chs o ans
gpn
ony.br

Ingot
iz gu on

pin
A
IR
Ya Rmgx
as as
tingx
I thot
Ho Cy Cy R

H E on one on Rmsx
l R H
n uz una Onyx

H E on one on 2Rmsk
ONYX
n k uz uz Omega
 Ingot
011
H d uz uz OM
k
amines
Using primary aliphatic
R Cha NK t HNon R Yz Oh 1 Nz
i alcohol
famine caitiff yo

Q What are the products when acetoacetic

ester reacts with enmethyl magnesium
halide followed by hydrolysis

acetoacetic alien
Iko ans

Ko ans Its nigh 7

acidic
n
no ans
ing Cng

H2o

Iko Feng x
 oxoprocerse
R2
R2
R
R G Rs t co the r
I CHO
h

I KINI
R2
R
Rz
cH OH

fermentationycarbohyth
k t
4211201 t H2O 7 GHz06 611,206
sucrose glucose fructose

Zymase

26kg011 2 CO2

Phenol carbolic acid

Igpardinds
haloarenes DOW'S PROCESS
from
Cl
5Nat on
623K Her
NaOh
300atom
 fumbenzenesulp honicaid
OH
oleum Noon
I 50311
i ht
125 02

COfomdiazoniwmsalts CH Nantz t Hyo

Nth N
HU zu warm
aniline
t Nz
diazotisation reaction
rice
from CUMENE

Ctb Chs
I 1 OH
C o o H O
ay en
02 ay ht
ld
t Cy cry
tho
CUMENE CUMENE
HYDROPEROXIDE

cohds

Boilingpoints
in
point increases with increase
Boing
atoms due to vdw forces
no carbon
of
decreases with increase in
Boiling point
 y
branching in isomers due to decrease
in vdw forces with decrease in surface
area
alcohols and phenols
the boiling points of to the
are in comparison
higher hydrocarbon
other classes compounds like
of haloasenes
ethers haloaklomes of
due to
comparable molar masses

INTERMOLECULAR h BONDING
Fo
n n n
oh tip o
no o

alcohols and phenols

solubility of
in water is due to their ability
to H buds with water molecules
O
n M
n o
n
ay ay Ey
n
o H
I
h
in size
solubility decreases with increase
hydrophobic groups
of alkyl laryl
 b
Arrange the tolling in order
of increasing p
butan l ol butan z ol
pentan l
ol
TI Il
I
l ol methanol
ethanol propan 430N
Gaston q I
Tf Cztho

It e I It LILI
I
n Butane pantanal
Penton i ol TIL
1
I
ethoxyethane
Ff
IV 111 S L
Il

themicalproput
R o H can act both as electrophiles
nucleophiles

Alcohols as nucleophiles T O H bond will

be broken

r o d
r E n e
g
t ti
Alcohol as electrophiles c O bond will
be broken
protonated alcohols behave this way

R CY OH Ht R cuz 0112
Br N t
R R t H2O
CH z ctfu
Bv

H bond
I Reactions involving cleavage of o

Aciditygphendsandalcohol t
all alcohols andphenols
Reactionwithmet
react with active metals like Na k Alek

to corresponding alkoxideslphenoxides
give
and
Hz gas

2R o H 2Na ZR ENat t th f

2nd 2
G ch
I on t 3 1,0 Al 312
g
Aluminiumtest
tert butylalcohol
butoxide
 Oh ENat

z t 2Na z t 11
Sodium
phenol phenoxideyphenolate

On ENat
NaOh t 110
Sodium
phenol phenoxideyphenolate

alcohols
acidity of H
It is due to polar nature of o
bonds
Presence M or 11 groups
of which
increases e density on
oxygen
H bond
reduces the polarity of o
acidic strength decreases
thus

Race on
Icu ons c on

Ka arder
water
Alcohols are weaker acids than

H OH
Ag OH

cb 0M
cryDo
R
stronger conjugate base
 than water
Thus arson is weaker
Bronsted bases as
Alcohols act as

well
R o h t ti R 0th

acidityfphenol
Phenols are
t
stronger acids than

alcohols and water due to resonance

stabilised conjugate base phenoxideion
0 O O
0
O
o o
f
i

I H k ell l
g
fl l G I I let 1 I r

U
I M
In substituted phenols
enhance the acidic character
groups
of phenol while I and 1M groups
the acidic character
decrease
when
This effect is more pronounced
such a is at o or
p
group
position

Q Arrange
the following in increeny order of
 acid strength
1 2,46 trinitrophenol
I Propan l ol

3 nitophenol 3,5 dinitrophenol

TI It
I phenol I 4 methylphenol

Am 1C6c5C3C4

Esterification acids
carboxylic
Alcohols phenols react with
anhydride to
acid chlorides and acid
form esters
ER tho
AYR OEI I i Y R AYR o

IIE Ir E Alr o i r ricoon

Ayr oi
O

Y R
Mrid
Ayr o E r Ha
AYR OEI I
to neutralise
pyridine is used
the tee formed

Introduction acetyl Conscot

Acetylation of group
alcohols or phenols is called
group in
acetylation
 OOH COOH

OCOCH
OH
o
Ht
yc t CHCOOH
acetic anhydride
salicylic acid acetylsalicylic acid
ASPIRIN

c o bond
II Reactions involving cleavage of
phenols show thistype of reaction only
with 2n
OH
Zn dust
ZnO

Reactionwitht
R Oh t H X R X tho
HCl distinguishes
of alcohols with
Reactivity
them from one another LUCAS TEST

REAGENT conc HCl

LUCAS Zingy
alcohols are soluble in Lucas reagent but
their halids are not
with 30 alcohols turbidity is produced
immediately
with 2 alcohols turbidity is produced
after some time
with 10 alcohols no turbidity produced
 try
at noon
temp
Reactionary
PX 3R Xt typo
3 R on

Dehydration
Reagents one HzS0y or typos
nor catalysts like anhydrous 2nA
or
Miss
y d W c
tho
I l
n on heat

Relativeeasefdehydation 3072021

Mechanism

slept Formahnypnotonatedalcohol
H H
H O
I I n
E
fast
I I In
StepI formationyearbocation
H H
H

Y YA n Y Cfto Hao

Steps
eliminetimqproton tk c d t ti
cf o
 Oxidation dehydrogenation

o
H Y o h
g
p 9
These bonds will
break shy
very To

Oxidiyagents KMnoy ht Kenzo Int

anhydrous Cros PCC mild 0A

conc MNO heated Cu ek

Pcc Pyridinium chlorochromate

Oo Eno a

h on
dah
4 R
R cz Oy R 0 c o

i alcohol aldehyde carboxylic

acid
and K 20 11nF give
KMnon ht
R COOH directly from alcohols
To get aldehyde we use milder
0A like anhydrous Crg or PCC

Cros
R Cheon R CHO
I alcohol
W C R
R En R p
l lo
on
j alcohol
 30 alcohols don't undergo oxidation
instead they undergo elimination to give
alkene
cry 4h
11
I 10 C
cry c oh cry
I M
as
Under stronger reaction like conditions

strong 0A Kourou and elevatedtemp

various C C bonds take
cleavage of
mixture of carboxylic acids
place and
a

lesser number c atom

containing of
are formed
4 3 2 i conc KMnoy
cycoon cycoon
cry
Gg Uz f0 HYO Breaking
ofc2 CD

Chzczcoon H COOH

Breaky ga Cy
cu
Razon R CHO
0
i alcohol
as
Rzchon R c R
O 11
alcohol 0
uz
l uz
C OH
Cu Il
cry 07 Cry C
1 I
3 alcohol cry as
Oxidation glycols Periodic acid
of using
c c 11104
I 1
Oh 011

Upon treament with 11304 compounds containay 2 or

more oh or to group attached to

adjacent carbon atoms undergo oxidation with
cleavage c c bonds
of
11104
Example R CH CH R RCHO
I 1
oh OH 1 R CHO

204
R R RCOOH
Cy Cy
R COOH

R Ch c R 204
Reno t R'COOH
ton 11
o

CH 104 HCOOH
p CH CH R RCHO t
i 1
OH OH Oh R CHO

R
FC Cn R
11104
R R R'CHO
I 1 g
Oh Oh
11104
R CH CHE CH
1
p NO REACTION
I
017 On
Reachongphend t
Elechophilicaromaticsubstitution
Oh group activating
q o
p directing

0
Nitration on on
Noa
dit 11h03

o nitrophenol I
NOL

Both can be separated by steam p nihophenol

distillation as o nitrophened has less b p

due tointramolecular n bonding White
nitophend has intermolecular k
bad
p
OH OH

02N N2
conc 11h03

NOL

219,6 trinitrophenol
PICRIC ACID