m tm tm tm t

ax ax ax ax
pl pl pl pl
us us us us
5 5 5 5

@ @ @ @
re re re re
sp sp sp s
ec ec e ct
pe
ct
m tm tm m
ax ax ax insTTre
ax
pl pl pl pl
us us us us
5 5 5 5

@ @ @ @
FOR LAKSHYA JEE 2023 FREE : CLICK ME

re re re re
sp sp sp s
ec ec e ct
pe
ct
m tm tm m
ax ax ax ax
RM pluss

JOIN NOW
pl pl pl pl
us us us us
5 5 5 5

@ @ @ @
re Search Doyish Sou PanTclegram re re re
Lalkhya E2023 Free
s
Page 1 of 37

sp sp sp p
 Page 2 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
@

@
Alcohols, Phenols
2 and Ether
5

5
us

us

us
pl

pl

pl
ax

ax

ax
INTRODUCTION (6) Secondary alcohols: When the carbon bearing the
tm

m
(ALCOHOLS AND PHENOLS) OH group is itself attached to two other carbon atoms,
ct

ct
Cg.propan-2-ol,
e

e
An alcohol contains one or more hydroxyl (OH)
CH-CH-(OH)-CH,.
sp

sp

sp
groups (s) directly attached to aliphatic carbon atom (s), whilea
(c)Tertiary alcohols: When the carbon bearing the -OH
re

re

re
phenol contains-OH groups (s) directly attached to aryl carbon
group is itself attached to three other carbon atoms, e.g.
@

@
atoms (s).
2-methylpropan-2-ol,
Classification of Alcohols and Phenols
CH-C-(CH)
On the basis of the number of -OH groups attached, alcohols OH
and phenols may be classified as:
L Monoh ydric Alcohol Which contains only
-
5

5
one-OH group per molecuie.
o-
us

us

us
Il. Dihydric Alcohol Which contain two-OH groups per
-

.
pl

pl

pl
molecule.
ax

ax

ax
Trihydric alcohol-Which contains three-OH groups per
Primary Secondary Tertiary
tm

tm

molecule.
tm
(n Allylic alcohols: In these alcohols, the -OH group is
ec

ec
CH,-OH CH,-OH
attached to a sp' hybridiscd carbon next to the
sp

sp

sp
CH-OH CH,-OH CH-OH carbon-carbon double bond, that is to an allylic
re

re

re
carbon. For example
CH,-OH
@

@
Monchydric Dihydric Trihydric
OH OH QH
OH CH-CH-CHOH CH-CH-OH CH,-CH-t-OH

OH
5

OH Tertiary(3)
us

us

us

Primary(T) Secondary (2)

Monohydric Dihydric Trihydric
pl

pl

pl

Monohydric Alcohols can be further classified based upon thec (ii) Benzylic alcohols: In these alcohols, the -OH group
ax

ax

ax

hybridisation state of the carbon atom to which the hydroxyl is attached to a sp-hybridised carbon atom next to
tm

tm

tm

group is attached an aromatic ring. For example

1. Compounds containing
COH bond: In this class of
ec

ec

alcohols, the-OH group is attached to a sp' hybridised

sp

sp

sp

carbon atom of an alkyl group. They are further classified

re

re

re

as follows:
@

() On the basis of number of carbon atoms attached to

the carbon atom bearing the -OH group:
Primary Secondary Tertiary
(a) Primary alcohols: When the carbon
bearing the -OH group is itselfattached to only one Allylic and benzylic alcohols may be primary.
other carbon atom, as in Ethanol, CH-CH-OH. secondary or tertiary.
5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 3 of 37
t

ct

ct
pe

pe

p
2. Compounds FOR LAKSHYA JEE
containing COH bond:2023 alcohols:
TheseFREE 2. Nomenclature
CLICK ME of phenols: The simplest hydroxyi

s
contain OH group bonded to a carbon-carbon double

re

re

re
derivatives of benzene is called phenol, a trivial name,
bond i.e., to a vinylic carbon or to an aryl carbon. These which has been accepted as its TUPAC name. Dihydroxy

@
alcohols are also known as vinylic alcohols. derivatives are named as 1,2-, 1,3-,or 1,4-benzene diol
Vinylic alcohol: CH, = CH-OH as under
OH
Hydroxyl derivatives of toluene are named as 2-Methy,
OH CH 3-Methyl, 4-Methyl phenol for o-, m-, and p- cresol,
Phenols: respectively.
5

5
us

us

us
OH CH CH, CH,
pl

pl

pl
IuPAC NOMENCLATURE OF ALcOHOLS AND OH
ax

ax

ax
PHENOLS
tm

m
OH
1. Nomenclature of Alcohols: An alcohol is named after the OH
ct

ct
TUPAC name of the hydrocarbon containing corresponding Common name Phenol o-cresol m-cresol P-Cresol
e

e
number of carbons. The last 'e' is dropped form the IUPAC JUPAC names Phenol 2-Methyl 3-Methyl 4-Methyl
sp

sp

sp
name of the hydrocarbon and is replaced by the suffix 'ol'. -phenol phenol -phenol
re

re

re
For example, the CHCH,CH,OH is named as propane-"ec
+ol"= propanol. Polyhydric alcohols are named after the
@

@
H
corresponding hydrocarbon, without removing the last OH
e', and denoting the number of-OH groups by prefixing
di, tri, tetra etc. before ol. The positions of-OH groups are
denoted by numerals 1,2, 3 etc. keeping in mind the lowest OH OH
sum rule. For cxample, CH,CH(OH)CH,OH is named as Common name Catechol Resorcinol Dihydroquinone or
propane-1,2-diol. IUPAC Benzene-1,2- Benzene-1,3- quinol, Benzene-1,4
5

5
Cyclic alcohols are named using the prefix cyclo and diol diol diol
us

us

us
considering the-OH group attached to C-1.
pl

pl

pl
OH OH CHARACTERISTICS OF THE -OH
ax

ax

ax
CH, FUNCTIONAL GROUP
tm

tm

tm
The characteristics of the-OH functional group are discussed
ec

ec
as under:
Cylohexanol 2-Methylcyclopentanol
sp

sp

sp
The-OH group in alcohols: The--oH bond in alcohols
Compound
re

re

re
Common IUPAC is between an sp' hybridizded oxygen of the
name name
@

@
CHy OH Methyl Methanol -OH group and an sp' hybridized carbon. The bond angle
alcohol (108.9°) is slightly less than the expected 109 28'. The
CHy-CH-CH-OH n-Propyl Propan-1-ol repulsion between the 2 lone electron pairs on oxygen is
alcohol
CH-CH-OH Isopropyl Propan-2-ol the reason for this decrease in the
alcohol -0-H bond angle.
CH CH
5

.The-OH
us

us

us

CH-CH-CH-CH-OH n-Butyl Butan-1-ol group in Phenols: The-¢-OH bond in phenols

alcohol
pl

pl

pl

CH3 Isobutyl is between an sp* hybridised oxygen of the

ax

ax

ax

alcohol Methylpropa -OH group and an sp? hybridised carbon. Here the bond
n-1-ol
HO-HC-CH-CH angle is 109°. In phenols, the C-Obond has a partial double
tm

tm

tm

CH-CH-CH2-CH Sec-ButylButan-2-01 bond character, on account of the conjugate system (a

ec

ec

alcohol
double bond alternating with an unshared electron pair i
OH
sp

sp

sp

p-orbital ofoxygen).
CH tert- Butyl 2-
re

re

re

alcohol Mcthylpropa
n-2-o1 142 pm 96pm 109°
@

CH-C-OH
CH
CH-CH-CH2 Glycerol Propane-
108.9 136pm
1,2,3-triolI Methanol Phenol
OH OH OH
5

-FULL CoURSE STUDY MATERLALJEE-XIL

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 4 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
PREPARATION OF ALCOHOLS

re

re

re
CH-CH-CH,+H-BH, CH CH-CH4

@
Alcohols may be preparcd by the following methods H BH,
L From Alkenes: The following processes may be employed
for converting alkenes to alcohols. CH-CH=CHi(CH.CHCH,),BH
1. Byacid catalysed hydration: Alkenes react with water
in the presence of acid as catalyst to form alcohols. In di-n-Propyl borane
case of unsymmetrical alkenes, the addition reaction
CHCH-CH
5

5
(CH,CH,-CH,)B
us

us

us
takes place in accordancc with Markovnikov's rule.
tri-n-Propylborane
pl

pl

pl
ax

ax

ax
3H,0,/OHr
3CH-CHCH,OH+B(OH),
tm

m
OH H
Propan-I-ol
ct

ct
In each addition step, the boron atom is attached to
e

e
CHCH=CH+H,O CH-CH-CH
sp

sp

sp
the sp? carbon atom that is bonded to greater number
re

re

re
OH of hydrogen atoms. The hydrogen atom is transferred
from boron atom to the other carbon of double bond.
@

@
Note: Industr ial alcohols are produced, by passing
alkene through H,SO, at high temperature and Thus, it is an anti-Markovnikov's addition. During
pressure. The acid is diluted and treated with steam oxidation of trialkyl borane, boron is replaced by
to release the alcohol. -OH group. The yield ofalcohol is excellent and the
product is casy to isolate.
MECHANISM Note: Carbocation is not formed in this reaction so
5

5
The mechanism of the reaction involves the following three carbocation rearrangement is not possible.
us

us

us
steps: 3. Oxymercuric-demercuric Hydration reaction
pl

pl

pl
Step 1: Protonation of alkene to form carbocation by
ax

ax

ax
R-CH CH R-ÇH-CH, (alcohol)
electrophilic attack of H0'.
tm

tm

tm OH
HO+ H >H,0*
ec

ec

H
sp

sp

sp
+H,
R-CH+Hs0CH RC
re

re

re
of water on carbocation. Hg-0--CH,
@

@
Step: 2 Nucleophilic attack

A HH
nu

Step 3: Deprotonation to form an alcohol.

Nab
R-CH-CH HO R-CH-CH,
5

5
us

us

us

H OH
R-CH-CH, CHs-0--CH,
OH
pl

pl

pl

+H0
ax

ax

ax
tm

tm

tm

Note:- Carbocation Rearrangement is possible in this Note: Carbocation is not formed in this reaction so
ec

ec

reaction. carbocalion rearrangement is not possible.

sp

sp

sp

2. By hydroboration - oxidation: Diborane, B,H, is an Over all process appears to be markonikov's addition
electron deficient molecule and BH, units can be added water.
re

re

re

of

to alkenes such that boron is attached to the Carbon Example 1: 1so-butylene when subjected to hydroboration oxi-
@

bearing greater number of hydrogen atoms. This is dation reaction yields

contrary to Markovnikov's rule. Trialkyl boranes, (1) sec-butyl-alcohol
formed as a result of addition, can be oxidized by
(2) Tert-butyl alcohol
HO, in alkaline medium to corresponding alcohols.
ALcOHOLS, PHENOLS AND ETHER 115
5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 5 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
3) Iso-butyl alcohol

@
NaBH
4) n-butyl alcoho! Gii) ?
OH
Ans. (3) Iso-butyl alcoho
L From AIkyl Halides: When alkyl halides are treated with
aq, KOH or aq. NaOH or moist Ag,O, alcohols are formod. LiAH7
OH
5

5
R-X+OH R-OH+X
us

us

us
2. Meerwein-Ponndorf-Verley Reduction
pl

pl

pl
IIL. From carbonyl compounds: Reduction of Carbonyl MPV Reduction):
ax

ax

ax
Compounds, Carboxylic Acids and their Derivatives:
tm

m
Its a name reaction of reduction of alcohol
ct

ct
R-C-H ed, agent
R-CHOH
e

e
sp

sp

sp
OH Ketones can be reduced to secondary alcohols with

R-C-R gR-H- aluminium isopropoxide in 2-propanol solution.

re

re

re
R
@

@
OH
R-C-ORed.agen R-CH,OH+R'-OH [(CH,),CHO]Al
C=0+ CH CH-CH

R-C-X R-CH,OH R
CH-OH + (CH,),C=0
R
5

5
us

us

us
R-C-O--R- 2R-CH,OH
3. From Grignard reagents: Grignard reagents (RMgX are
pl

pl

pl
ax

ax

ax
Table: Reducing nature of different reagents alkyl or aryl magnesium halides. The C- Mg bond in
Grignard reagent is a highly polar bond as carbon is
tm

tm

tm
Product LiAIH/H,O NaBHB,H,THF
Group
CHOHD H/Pt| electronegative relative to electropositive magnesium. Due
ec

ec

-CHOH| Yes Yes Yes Yes

to this polar nature of C-Mg bond, Grignard reagents are
sp

sp

sp
C-0 >CH-OH Yes Yes Yes Yes very versatile reagents in organic synthesis.
re

re

re
Yes No Yes Yes
-coOH CHOH Alcohols are produced by the reaction of Grignard reagents
@

@
with aldehydes and ketones.
La CH,OH Yes Yes No Yes

R,oRoH Yes No Yes Yes

8 OMg'x
-OH+Mg(OH)x
-CHOH+ Yes No No Yes *
oR R-OH R
5

Adduct Alcohol
us

us

us

>CH-CH< No Yes Yes

>0-C< No
(LiAIH, reduces)
pl

pl

pl

Thus, the overall reactions are as follow

CConly
ax

ax

ax

when it is
conjugated with
HCHO+RMgX > RCH,OMgX0
tm

tm

tm

Phenylic system
RCH,OH +Mg(OH)X
ec

ec

Example 2: Find the product of given reaction

sp

sp

sp

R
re

re

re

CH i)B,H /THF
RCHO+R 'MgX -> R-CH-OMgX
@

CH (i)H,0,/0H

R
CH HTH,O,,,
-CH -CKH _iOR-CH-OH +Mg(OH)A

116
5

FuLL COURSE STUDY MATERIALJEE-XII

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 6 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
PREPARATION OF PHENOLS

@
R In the laboratory, phenols may be prepared from benzene
RCOR+R'MgX -> R-C-OMgX derivatives by any of the following methods:
L From aryl sulphonic acids: An aryl sulphonic acid yields
R
the corresponding phenol on heating with molten sodium
hydroxide at 570-620K
5

5
us

us

us
R So,Na ONa OH
pl

pl

pl
SO,H

HaOR-C-OH+ Mg(OH)X
ax

ax

ax
2NaOH_
+NaOH| 573K
tm

m
R
ct

ct
IL From haloarenes: Chlorobenzene is hydrolysed by
e

e
Note: The reaction produces a primary alcohol with
sp

sp

sp
treating it with NaOH at 623K and 300 atmospheric
HCHO, secondary alcohol with any other aldehyde, and a
pressure. Phenol is obtained by acidification of sodium
re

re

re
tertiary alcohol with a kctone. phenoxide.
@

@
4. From carboxylie acid and their derivatives:

CI ONa
OH
R--Z+R -Mgx R- -
R+Mg
X +NaOH 623K HC
5. From epoxides: 300atn
5

5
us

us

us
OMgx
mgx CH,-CH-CH
IIL Hydrolysis of diazonium salts: A diazonium salt is formed
pl

pl

pl
CH,-CH by treating an aromatic primary amine with nitrous amine
ax

ax

ax
with nitrous acid (NaNO,+HCI) at 273-278K temperature.
tm

tm

tm
Diazonium salts are hydrolysed to phenols on treating
OH with dilute acids.
ec

ec
,OH
HoI CH, -H-CH *
M9x
sp

sp

sp
NH, N=NCI OH
re

re

re
6. Hydrolysis of Ether: Ether undergo acid hydrolysis with NaNO,+HCl
@

@
dilute H,S0, under pressure to give corresponding alcohols. 273-278K HO
wam +N,+HCI

R-0-R+H0 R-OH+R-OH Aniline Benzene diazonium

Example 3: Ketones can be converted to tertiary alcohols chloride
by
(1) Reduction V Fromcumene: Phenol was first isolated from coal tar. Now
5

(2) Oxidation a days, it is manufactured from the hydrocarbon, cumene.

us

us

us

3) Reaction with Grignard reagent Cumene, isopropylbenzene is oxidised in presence of air

pl

pl

pl

4) All of these to cumene hydroperoxide. It is converted to phenol and

ax

ax

ax

Ans. (3) Reaction with Grignard reagent acetone by treating it with dilute acid. Acetone, a by-
tm

tm

tm

Example 4 : In the sequence of reactions, product of this reaction, is also obtained in large quantity
ec

ec

by this method.
MgBr +CH, CH, - A 1,01HB
CH,
sp

sp

sp

CH,

CH-C-O-0-H OH
re

re

re

The Product B is CH-CH

@

(1) Benzyl alcohol

(2) 2-phenyl ethanol |H HO +CHCoCH,
3) 1-phenyl cthanol
4) Quinol CumenC Cumene
Ans. (2) 2-phenyl ethanol hydroperoxide

11
5

ALcOHOLS, PHENOLS AND ETHER-

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 7 of 37
t

ct

ct
pe

pe

p
FORSynthesis:
LAKSHYA JEE 2023 FREE : CLICK MEsolubility of alcohols and phenols in

s
V Grignard's The water is due

re

re

re
their abilityto form hydrogen bonds with water moleculest

@
CHMgBr+02 C,H,ÕMgBr The solubility decreases with inerease in the
size of
hydrophobic group (R).

HOIH CH,OH+ Mg OH
5

5
VL From Salicylic Acid: CH-CH-CH- H
us

us

us
pl

pl

pl
OH OH
ax

ax

ax
-COOH -cOONa
tm

m
+NaOH- + NaOH
ct

ct
TRAIN YOUR BRAIN
e

e
sp

sp

sp
OH
Example 5: Arrange the following as mentioned
re

re

re
CaO, A
-Na,coO OH
@

@
(a)) i)
PHYSICAL PROPERTIES OF ALcOHOLS AND
PHENOLs
OH
Following are the physical properties of alcohols and phenols:
(increasing order of boilingpoints)
5

5
Alcohols and phenols consist of two parts, an alkyl/aryl
us

us

us
group and a hydroxyl group. The properties of alcohols
pl

pl

pl
and phenols are due to the -OH group. The alkyl and aryl
ax

ax

ax
groups modify these properties.
-OH HOO>oH
tm

tm

tm
.The boiling points of alcohols and phenols increase with
OH OH
ec

ec

increase in the number of carbon atoms (due to increase in

sp

sp

sp
van der Waals forces). In alcohols, the boiling points Gii)HO- (iv) HO
decrease with increase in branching (decrease in vander
re

re

re
Waals forces due to decrease in surface area).
@

@
increasing order of solubility in water)
--- Sol. (a) 6i) <(iv) <(i) < (ii)
H-0--- H-0 H-Q-
(b)i)<iv)<(ii)<(i)
Para isomer is more susceptible to form inter-molecular
H-bond with water and therefore more soluble.
Example 6: Arrange the following in increasing order of their
5

5
us

us

us

i) Solubility and (i) Boiling Point

pl

pl

pl

R-0H-0-H-0-- H-O OH OH
ax

ax

ax

H R
tm

tm

tm

The -OH group in alcohols and phenols contains a

OJ
ec

ec

hydrogen, bonded to an electronegative oxygen atom.

sp

sp

sp

Therefore, it is capable of forminghydrogen bond as showm

OH
re

re

re

in the above figurc. OH

It is due to the presence of Intermolecular hydrogen
@

bonding that alcohols and phenols have higher boiling (ii) (iv)
points than the corresponding other classes of compound.,
namely, hydrocarbons, ethers and haloalkanes/haloarenes
ofcomparable molecular masses. Sol. Solubility )> (i)>
(i)> (iv)
Boiling Point (iv)> (Gii)> (i)> ()
5

118
us

us

us

FuLL CoURSE STUDY MATERIAL JEE-XI

pl

pl

pl
ax

ax

ax
m

m
 Page 8 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
CHEMICAL REACTIONS OF ALCOHOLS AND fact, alcohols and phenols are Bronsted acids i.e., they

@
PHENOLS can donate a proton to a strong base (B:).
.The bond between O-H is broken when alcohols react as
nucleophiles : +48-R » B-H 0-R
Base Alcohol (Conjugate Alkoxide ion
acid (Conjugate
R-O-H +
-R--RO¢+H (Acid)
5

5
base
us

us

us
pl

pl

pl
On treating an alkoxide with water, the starting alcohols is
.The bond between C-O is broken when they react as
ax

ax

ax
obtained.
electrophiles. Protonated alcohols react in this manner.
tm

m
Protonated alcohols as electrophiles R-Q+ H-0-H> R-0-H +OH
ct

ct
Base Acid Conjugate Conjugate
e

e
acid base
R-CH-ÖH+H> R-CH-OH
sp

sp

sp
This reaction shows that water is a better proton donor
re

re

re
than alcohols. In other words, alcohols are weaker acids
@

@
Br +CHr QH-Br-CH,+H,O than water. Also, in the above reaction, we note that an
R R alkoxides ion is a better proton acceptor than hydroxide
ion, which shows that alkoxides are stronger bases.
Based on the cleavage of O-H and C-0 bonds, the
The acidic character of alcohols is due to the polar
reaction of alcohols and phenols may be divided into two
0-H bond. An electron-releasing group (CH) increases
groups:
5

5
electron density over the oxygen atom tending to decrease
us

us

us
1. Reactions involving cleavage of O-H bond
the polarity ofO-Hbond. This decreases the acid strength.
() Reaction with Metals: Alcohols and phenols react
pl

pl

pl
For this reason, the acidic strength of alcohols decreases
with metals such as sodium, potassium, and aluminium
ax

ax

ax
in the following order
to yield corresponding alkoxides/phenoxides and
tm

tm

tm
hydrogen.
ec

ec

2R-0-H+2Na >2R-0-NatH, K
R-CHOH> CHOH> R¢OH
sp

sp

sp
CH CH,
R R
re

re

re
Primary Secondary Tertiary
6CH-C-OH+2AI >2 CH--0-Al-O--CH+3H,
@

@
CH, CH CH
Obviously, the basic strength of their alkoxides follows
CH-C-CH, the reverse order.
CH
R
Aluminium tert. butoxide R
R
CH- >R-CH
5

5
us

us

us

OH ONa Alcohols act as Bronsted bases as well. It is due to the

pl

pl

pl

presence of unshared electron pairs over oxygen, which

22Na-2JH,
ax

ax

ax

makes alcohols proton acceptors.

tm

tm

tm

Phenol Sodium phenoxide H

R--H +H,SO-R-0-H+HSO,
ec

ec

In addition of this, Phenols react with aqueous sodium

hydroxide to form sodium phenoxides.
sp

sp

sp

A note on Acidity of Phenols: The reaction of phenols

re

re

re

OH ONa
with aqueous sodium hydroxide indicates that phenols
@

2 J+NaOH
-UH0 are stronger acids than alcohols and water. Let us examine
how the hydroxy! group attached to an aromatic ring is
Sodium phenoxide
more acidic than the hydroxyl group attached to an alkyl
A note on acidicnature of alcohols: The above reactions group. The ionizaton of an alcohol and a phenol takes
nature. In
show that alcohols and phenols are acidic in place as follows:
5

ALcOHOLS, PHENOLS AND ETHER- 15199-

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 9 of 37
t

ct

ct
pe

pe

p
-
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
R-0-H R-+H

@
OH
OH OH
NO,
O)
5

5
The greater acidity of phenol is due to the stability of the
us

us

us
OH OH
phenoxide ion, which is resonance stabilized as shown
pl

pl

pl
below.

O
ax

ax

ax
CH
tm

m
ct

ct
OCH,
e

e
sp

sp

sp
Sol. (a) (i)> (ii)>i)
re

re

re
I IV (b) (ii)> (i)> (ii)> (iv)
@

@
In substituted phenols, the presence of electron
withdrawing groups at ortho and para positions such as
nitro group, stabilizes the pnenoxide ion resulting in an
-NO, is stabilizing -o by strong electron

increase in acid strength. It is due to this reason that ortho withdrawing nature, CH, is destabilizing CHO by
and para nitrophenols are more acidic than phenol. On the electron donating nature (+1) and -0CH, is also
5

5
other hand electron releasing groups such as alkyl groups, destabilizing CH,O due to electron donating nature
us

us

us
do not favour the formation of phenoxide ion-resulting in +R,-1)
pl

pl

pl
decrease in acid strength, Cresols, for examplc, are less (i) Esterification: Alcohols and phenols react with
ax

ax

ax
acidic then phenol. carboxylic acids, acid chlorides and acid anhydrides to
tm

tm

form esters.
tm
The reaction with carboxylic acid and acid anhydride is
ec

ec

QH QH OH OH carried out in presence ofa small amount of concentrated

sp

sp

sp
NO NO,
NO NO, sulphuric acid. The reaction is reversible, and therefore,
O
re

re

re
water is removed as soon as it is formed. The reaction with
@

@
acid chloride is carried out in presence ofa base (pyridine)
NO, NO so as to remove HCI. It also shifts the equilibrium to the

Electron releasing group such as alkyl groups does not

favour the formation of phenoxide ion resulting in decrease right hand side. The introduction of acetyl CH--group
in acid strength. in alcohols or phenols is known as acetylation.
5

5
us

us

us

OH OH OH
CH, CHH
RO-H+R-COOH ROCOR+ H20
pl

pl

pl

CH, CH,
ax

ax

ax

OH
tm

tm

tm

CH CH, R-C--H+H°>R'--OH->R-¢-OH- R-¢OH1

ec

ec

unsiion
state
OR OR
sp

sp

sp

Y
TRAIN YOUR BRAINS R--H
R
re

re

re

ROH R-C-OR
@

Example 7: Arrange the following in decreasing order of acidic (-H)

nature of
a) (i)FCCH,OH Reactivity of compounds for esterification
i)(CH),CCH,OH
(ii) FCH CH,CHOH Steric hindrance
oc Stability of Transition State
5

120 FULL COURSE STUDY MATERIAL JEE-XII

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 10 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
Reactivity order for of
3ROH+ PCI, 3RCI +HPO, (S2) (inversion

re

re

re
carboxylic: HCOOH> CHCOOH> CHCHCOOH configuration)

@
Alcohols: CHOH> CH,CH,OH> CH,CHCH,OH
ROH +PCI>RCI + POCI, + HCI(S,2)(inversion of
configuration)
ArOH+R-CoOH AOCOR'+H,0 The reaction with thionyl chloride is preferred as the
byproducts (SO,and HCI) formed are gases and are easily
ArOH/R-OH +(R'CO), O removed from the reaction mixture.
5

5
Ar/ROCOR'+R'COOH
us

us

us
R-OH+SOCnR-C+S0, + HCI (S2)
pl

pl

pl
R/ArOH+R"COCI (inversion of configuration)
nR/ ArOCOR'+ HCI
ax

ax

ax
.Acetylation of salicylic acid produces aspirin, which ii) Dehydration: Alcohols undergo dehydration to form
tm

m
possesses analgesic, anti-inflammatory and antipyretic alkenes (removal of a molecule of water on treating
ct

ct
properties. them with a protonic acid e.g. Conc. HSO, H,PO, or
e

e
catalysts such as anhydrous zinc chloride or alumina.
sp

sp

sp
ÇOOH COOH
re

re

re
OH ,OCoCH,
@

@
OH
+(CH,CO)0 +CH,COOH
Ethanol undergoes dehydration by heating it with
concentrated H,SO, at 443K.
Salicylic acid Acetyl salicylic
acid (Aspirin) CH,OH 443KCH, = CH2 +H,0
5

5
Secondary and tertiary alcohols are dehydrated under
us

us

us
2. Reaction involving eleavage of carbon-oxygen(C-0) bond milder conditions. For example:
pl

pl

pl
Reaction with hydrogen halides:
ax

ax

ax
OH
Most alcohols undergo Sl.
tm

tm

tm
(a) R-OH + HCI(g)A R-CI+ H,0 CH,CHCH
d3 440K CH-CH=CH2 +H,0
ec

ec
turbidity

Note : HC1+anhyd. ZnCl, is called Lucas reagent.

sp

sp

sp
Reactivity order ofAlcohol with Lucas reagent CH CH2
re

re

re
30>20> 1°
CH-C-OH
@

@
358K CH-Ë-CH-H,O
(TertiaryAlcohol can react with HCl even in absence
of ZnCL) CH
(b) R-OH +HBr R-Br+H20
(c) R-OH
+HI> R-1+H,0 The relative ease of dehydration of alcohols follows
Reactivity order of HX is HI> HBr>HCI the following order.
5

Tertiary aleohol> Secondary alcohol > Primary

us

us

us

Gi) Reaction with phosphorus trihalides: Alcohols are

converted to alkyl bromides by reaction with alcohol
pl

pl

pl

phosphorus tribromide
ax

ax

ax

A note on mechanism of dehydration of alcohols

3ROH+PBr, 3RBr+HPO, The dehydration of ethanol involves the following
tm

tm

tm

Alkyl iodides /Bromidcs are obtained by reacting an steps:

ec

ec

alcohol with iodine in presence of phosphorus. Step () Formation of protonated alcohol:

sp

sp

sp

ROH
ROH Re dP'hosphonus+ R-X
X2-l2,BrC
re

re

re

HHH
@

Alkyl chlorides are prepared by reacting an alcohol H- H+d

with thionyl chloride or phosphorus trichloride or
H¢Ó-H
phosphorus pentachloride.
R-OH+SOCl>RCI+sO, +HCI (Si) (Darzen's Ethanol Protonated alcohol
(Ethyl oxonium ion)
reaction) (retention of configuration)
5

121
us

us

us

ALcOHOLS, PHENOLS AND ETHER-

pl

pl

pl
ax

ax

ax
m

m
 Page 11 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
Dehydrogenation: When the vapours of a primary or a

re

re

re
Step (11) Formation of carbocation: It is the slowest

@
step and hence, the rate determining step of the secondary alcohol are passed over copper heated at S73
reaction. K, an aldehyde or a ketone is formed. Tertiary alcohols
undergo dehydration.

H- slow +H_O RCH,OH9RCHO+H

H
5

5
R-CH-R57RC-R+H2
us

us

us
Note: Carbocation Rearrangement is possible in this
OH
pl

pl

pl
reaction.
ax

ax

ax
Step (11) Formation of ethene byelimination of Proton:
CH3 CH
tm

m
ct

ct
H CH-C-0H 573K CH -=CH2+H,0
e

e
sp

sp

sp
Ethene CH3
re

re

re
SAYTZEFF RULE Distinction Between 1°, 2° and 3° Alcohols
@

@
1. Lucas Test: Any alcohol is treated with Lucas reagent
A reaction that produces an alkene would favour the formation
of an alkene that has the greatest number of substituents (HCI + anhyd. ZnC1,) at room temperature if
attached to the C=Cgroup. ) Solution becomes cloudy immediately, alcohol is 3°.
(i) Solution becomes cloudy after 5-min, alcohol is 2.
CH,CH-CH=CH, + HO (ii) In solution cloud does not form at room
CHCH H-CH, 1-butene (Minor product) temperature, alcohol is 1°.
5

5
CHCH=CH-CH, +HO
us

us

us
OH 2. Victor Meyer's Method:
2-butene
2-butanol major product
pl

pl

pl
R-CHOH R-CHIgNO
ax

ax

ax
(1-alcohol)
tm

tm

Example 8: Which of the following alcohols can be most casily

tm
dehydrated?
ec

ec

(1)CHOH (2) CH,-CH OH -HO

R-CH-NO, + HNO, R-C-NO,
sp

sp

sp
CH,
re

re

re
N
@

@
OH
CH, (Nitrolic acid)
(3)CH,-Ç-OH (4) CH,CHCHOH NaOH
CH blood red colour
v) Oxidation:
5

RCH-OH R,CH-1ARNO
us

us

us

CHOH 0H-6-HH-E-OH co, + H,O (2-alcohol)

pl

pl

pl

3°-alcohols can't be oxidised.

ax

ax

ax

Strong oxidising agent like KMn0, or K,Cr,0, cause -HO

RCH N0, + HNO, RÇ-NO
tm

tm

tm

maximum Oxidation as above.

NO
ec

ec

) If1°-alcohol has to be converted into aldehyde PCC

Pseudonitrol
+CHCl, or CrO, should be used among which PCC
sp

sp

sp

NaOH
+CH,Cl, is the best.
re

re

re

(ii) 2°-alcohol can con verted to ketone best by PCC blue colour
@

+CH,Ci, or CrO, or H,Cro, in aq. acetone (Jones

reagent). AgNO2
(iv) MnO, selectively oxidises the -OH group of allylic RC-OH RC-I R,C-NO,
(3°-alcohal)
and benzylic 1° and 2° alcohols to aldehydes and
ketones respectively HNO2
No reaction colourless
5

5
us

us

us

122 FULL CoURSE STUDY MATERIAL JEE-XI

pl

pl

pl
ax

ax

ax
m

m
 Page 12 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
MORE REACTIONS OF PHENOOLS

re

re

re
Industrially, picric acid isprepared by treating phenol,

1. Electrophilic aromatic substitution: The
-OH group
attached to the benzene ring in phenol activates it towards
electrophilic substitution. It also directs the incoming
group to ortho and para positions in the ring as these" i)
positions become clectron rich due to the electronic effect
5
@
first with conc. H,SO, which converts to phenol-2,
it
4-disulphonic acid. This yields picric acid on treating
it with conc. HNO,.
Halogenation: On treating phenol with bromine,
different reaction products are formed.

5
(plus mesomeric effect) caused by -OH group. (a) When the reaction is carried out in solvent of low
us

us

us
polarity such as CHCI, or CS, and at low temperature,

-a
pl

pl

pl
CO-H +0-H monobromo phenols are formed.
ax

ax

ax
The usual halogenation of benzene takes place in
tm

m
presence of a Lewis acid, FeBr, which polarises the
ct

ct
halogen molecule. In case of phenol, the Polarisation
e

e
IV V of bromine takes palce even in the absence of Lewis
sp

sp

sp
acid. It is due to the highly activating effect of -OH
Common electrophilic aromatic substitution reactions
re

re

re
group on the benzene ring.
taking place in phenol are as follows:
@

@
) Nitration: With dilute nitric acid at low temperature OH OH QH

(298 K), phenol yields a mixture of ortho and para Br,inCS, Br HBr
nitro phenols. 273K
Minor
Br
QH OH
5

5
OH Major (80%%)
NO
us

us

us
|Dilute HNO
pl

pl

pl
OH OH OH
ax

ax

ax
Br
0-Nitrophenol NO,
tm

tm

tm Br+Br +H
p-Nitrophenol
ec

ec

(b) When the reaction is carried out in aqueous

sp

sp

sp
The ortho and para isomers can be separated by steam medium (a polar solvent) i.e., bromine water, 2, 4,6
re

re

re
distillation, o-Nitrophenol is steam volatile due to tribromophenol is formed.
@

@
intramolecular hydrogen bonding while p-nitrophenol
OH OH
is less volatile due to intermolecular hydrogen
bonding which causes the association of molecules Br
agqueous
+3Br.
+5BT,
s0lution

Br
5

2,4,6-Tribromophenol
us

us

us

p-Nitrophenol 2. Kolbe's reaction: On reacting sodium salt of phenol with

pl

pl

pl

o-Nitrophenol
ax

ax

ax

carbon dioxide gas, ortho hydroxybenzoic acid is formed

With concentrated nitric acid, phenol is converted to as the main product.
tm

tm

tm

2,4,6-trinitrophenol. In this, nitration is accompanied

ec

ec

OH ONa'
by oxidation of phenol.
Na H
sp

sp

sp

eaangeent
re

re

re

OH
ON NO
@

Conc. HNO PA
CoOH
NO,
2,4,6 Trinitrophenol
(Picric acid) 2-Hydroxy benzoic acid
(salicylic acid)
5

5
us

us

us

ALcoHOLS, PHENOLS AND ETHER-

pl

pl

pl
ax

ax

ax
m

m
 Page 13 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
(i) Salol (with phenol)
3. Acylation and benzoylation:

re

re

re
OH

@
Acylation OH

CH,
cOOH +CH,OHHso,
-o-cA
CsHs-OH+CH,-C-CImidine CH,-O-C- Phenyl salicylate
Phenol Acetyl chloride Phenyl acotate (Salol)

Benzoylation Used as antiseptic

5

5
(a) If instead of chloroform, carbon tetrachloride is
us

us

us
Ph-OH+Ph--ClN0 Ph -OcOPh used, salicylic acid is formed. Some para isomers is
pl

pl

pl
also formed.
ax

ax

ax
ONa
4. Reimer Tiemann reaction: On treating phenol with H CC,
tm

m
chloroform in presence ofsodium hydroxide, a-CHO group aO
(O]"+CCI,
ct

ct
340 K
is introduced at ortho position of benzene ring. This
e

e
sp

sp

sp
reaction is known as Reimer Tiemann reaction. ONa
re

re

re
coONa
3NaOH(a4)
@

@
OH ONa
-3NaCI
CHC1,
CHCLt ag NaOH OH
Dil. H,SO
COOH
Intermeediate
5

5
In this reaction ®CCl is formed as intermediate
us

us

us
ONa OH
CHO which attack on benzene ring as electrophile.
cHO
pl

pl

pl
NaOH Example 9: n Reimer Tiemann reaction dichlorocarbene acts as
ax

ax

ax
(a) Nucleophile (6) Electrophile
Salicylaldehyde
tm

tm

tm
(c)Freeradical (d) All of these
ec

ec

The intermediate substituted benzal chloride is hydrolyzed Ans. (b) Electrophile

in presence of alkali to produce salicylaldehyde. Example 10: The following reaction is known as
sp

sp

sp
CHCI,/NaOH
re

re

re
Mechanism:
Phenol Salicylaldehyde
H
@

@
CHCI >:CCl, (a-elimination) + KCI + H,O (a) Gattermann aldehyde synthesis
QH (b) Sandmeyer's reaction
OH. OH
H CHC (c) Kolbe's reaction
HO0,
(d) Reimer-Tiemann reaction
Ans. (d) Reimer-Tiemann reaction
5

benzal chloride
us

us

us

5. Reaction of phenol with zine dust: Phenol is converted to

benzene on heating with zinc dust.
OH
pl

pl

pl

OH
QH
H OH
ax

ax

ax

OH H0),
tm

tm

tm

Zn Zn +ZnO
ec

ec

Salicyaldehyde
6. Oxidation: Oxidation of phenol with chromic acid produces
sp

sp

sp

(i) Methylsalicylate from methanol and Salicylic a conjugated diketone known as benzoquinone. In the
Note:
re

re

re

presence of air, phenols are slowly oxidised to dark coloured

acid
mixtures containing quinones.
@

H
COO CH,OH S04
oc OH
Na,Cr,O
few drop H,SO
Methy! Salicylate

oil of wintergeen benzoquione

5

5
us

us

us

124 - FULL COURSE STUDY MATERIALJEE-XII

pl

pl

pl
ax

ax

ax
m

m
 Page 14 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA
C-O Bond: JEE 2023 FREE : CLICK ME

s
7. Reactions due to

re

re

re
8. Coupling with Diazonium Salts:
) Reaction with PCl

@
CHOH + PCI,> CH,Cl+POCI, +HCI H,N,CI + CH,OH0-5C
pH 9-10
3CHOH+ PCl, > P(OCsHs)3 + 3HCI
Triphenyl phosphate

The yields of CH,Cl is very poor due to the formation

of triaryl phosphate.
N=N-oH
5

5
p-Hydroxy azobenzene
us

us

us
(ii) Reaction with Ammonia: (An orange dye)
pl

pl

pl
CHsOH+ NHg 9. Test for phenol
CgHNH2+H,O
ax

ax

ax
Phenol 573 K Aniline ) Neutral FeCl, test > Aqueous solution of phenol gives
tm

m
(ii) Reaction with Zinc Dust: a violet colouration with FeCl.
ct

ct
Gi) Br, water test Aqueous solution of phenol gives a
e

e
CH OH+ Zn CgHg + ZnO
sp

sp

sp
Phenol Benzene yellow precipitate of 2, 4, 6-tribromophenol with bromine
re

re

re
water.
iv) Reaction with Neutral FeCl,: ( Test for phenol)
@

@
ii) Phenol gives Liebermann's nitroso reaction.
3CH,OH + FeCl (CeHsO)Fe +3HCI
NaNO2
Ferric phenoxide
(Violet)
(in
Phenol
conc. H2SO,)eNCess of water
Red colour >blue colour

(iv) Friedel-Crafts Alkylation and Acylation: Phenol

Example 11: Electrophilic substitution in phenol takes place at
undergo both these reaction to form mainly p-isomer.
(a) Ortho and para positions
5

5
us

us

us
() Meta-position
pl

pl

pl
OH H (c) Ortho-position
ax

ax

ax
() Para-position
+CH,CI Anhyd. AlCl Ans. (a) Ortho and para positions
tm

tm

tm
Phenol Example 12: ldentify the product Z in the following sequence of
ec

ec
CH,
(Major product) reactions
sp

sp

sp
P-Cresol
OH NaOH,X4-1
re

re

re
CO, y
HO, z
@

@
atm
410 K
OH
(a) Aspirin (6) Salicylaldehyde
(c) Benzoic acid (d) Salicylic acid
o-Cresol (Minor product) Ans. (d) Salicylic acid
5

5
us

us

us

OH OH
Example 13:Zinc Powder +|
pl

pl

pl

+CH,COCI Anhyd. AlCl

ax

ax

ax
tm

tm

tm

In the above reaction the product X will be

ec

ec

QH (a) Benzaldchyde (b) Benzene

OH
sp

sp

sp

()Anisole (d) Phenyl Acetate

coCH,
re

re

re

Ans. (6) Benzene

@

COCH
ETHERS
Hydroxy acetophenone In ethers, an oxygen atom is attached to two carbon atoms of
two alkyl or an alkyl and aryl or two aryl groups.

ALCOHOLS, PHENOLS AND ETHER- 125

5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 15 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
PREPARATION OF ETHERS

re

re

re
CLASSIFICATION OF ETHERS

@
Ethers are classified as simple or symmetrical, ifthe alkyl or aryl I. By dehydration of alcohols
groups attached to the oxygen atom are the same, and mixed or
Alcohols undergo dehydration in presence of protonic acids
unsymmetrical, if the two groups are different. Diethyl ether,
HOC H, is a symmetrical ether whereas C.H,0CH,, and (,SO, HPO). The formation of reaction product, alkene or
CHOCHare unsymmetrical ethers. cther depends on the reaction conditions. For example, ethanol
is dehydrated to ethene in presence of sulphuric acid at 443 K
5

5
NOMENCLATURE OF ETHERS
us

us

us
and at 413 K; Ethoxyethane is the main product.
Common name ofethers follow after the names of alkyl/aryl groups
pl

pl

pl
written as separate words in alphabctical order. The word ether is
ax

ax

ax
added at the end. According to IUPAC nomenclature, ethers are
CH,
443K
= CH,
tm

m
regarded as hydrocarbon derivatives in which a hydrogen atom, CH,CH,OH-
ct

ct
is replaced by an alkoxy group-OR or -OAR group, the larger HSO,C.H,OCH,
e

e
sp

sp

sp
group (R) being chosen as the parent hydrocarbon. 413K
re

re

re
Compound Common Name IUPAC name
The dehydration of secondary and tertiary alcohols to get
@

@
CHOCH Dimethyl ether Methoxymethane corresponding ethers is unsuccessful as alkenes are formed
CaH,OCH Diethyl ether Ethoxyethane easily in these reactions.
CHOCH:CH:CH Methyl n-propyl ether1-Methoxypropane The formation of ether is a nucleophilic bimolecular reaction
CoHOCHs Methylphenyl ether Methoxybenzene (S2) involving the attack of alcohol molecule on a protonated
(Anisole) (Anisole)
alcohol, as indicated below:
5

5
CcHsOCHCH
us

us

us
Ethylphenyl ether Ethoxybenzene
(Phenctolc)
pl

pl

pl
CcHsO(CH:)-CH Heptylphenyl cther 1-Phenoxyheptane ) CH-CH,-0-H+H CH,-CH, -*0-H
ax

ax

ax
CH,0-CH-CH3 Melhyl isopropyl 2-Methoxypropane
tm

tm

cther
tm
CH H
ec

ec

CsHs-0-CH, -CH2-CH-CH Phenylisopentyl cther i)CHCHCHFH CHCH ÖCH.CH,+H,O

sp

sp

sp
metylbutoxybenzene
CH
re

re

re
CH-0-CH-CH-OCH 1,2
@

@
Dimethoxyethane
(Gin)CH,CH-0-CH,CH,CH,CH,-0-CH,CH,+H
2-Ethoxy-

1,1
H,C CH
OCH, dimethylcyclohexane Acidic dehydration of alcohols, to give an alkene is also
associated with substitution reaction to given an ether.
5

This method is suitable for the preparation of ethers having 1°

us

us

us

alkyl groups only. The dehydration of 2 and 3° alcohol give

Structure of functional group for ether
pl

pl

pl

.
alkenes as major product.
ax

ax

ax

In ethers, the four clectron pairs, i.e., the two bond pairs and two
lone pairs of clectron around oxygen are arranged approximatcly Williamson synthesis of ethers
tm

tm

tm

in a tetrahedral arrangement. The bond angle is C-O-C slightly t an important laboratory method for the preparation of
1s
ec

ec

greater than he tetrahedral angle due to the repulsive interaction symmetrical and unsymmetrical ethers. In this method, an alky
sp

sp

sp

between the two bulky (-R) groups. The C-O bond length (141pm) halide is allowed to react with a sodium alkoxide.
re

re

re

in ethers is almost the same as in alcohols

141pm R-X+R-ONa>R-0-R+ NaX(SN2)
@

Ethers containing substituted alkyl groups (secondary or.

HH tertiary) may also be prepared by this method. The reaction
involves a nucleophilic substitution ofhalide ion
by an alkoxide
Methoxymethane ion.
5

FULL COURSE STUDY MATERIAL. JEE-XI

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 16 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
PHYSICAL PROPERTIES OF ETHERS

re

re

re
CH,
CH

@
CH-Br+Na-Q-¢CHCH-O-C-CH+NaBr The C-O bonds in ether are polar and thus ethers have a
&H, net dipole moment. The weak polarity of ethers do not
CH
appreciably affect their boiling points which are
Good results are obtained ifthe alkyl halide is primary. Ifa tertiary comparable to those ofthe alkanes of comparable molecular
alkyl halide is used, an alkene is the only reaction product and mass but are much lower than the boiling points of alcohols.
Ethers containing upto 3 carbon atoms are soluble in water
5

5
no ether is formed. For example, the reaction of CHONa with
us

us

us
(CH)CBr gives exclusively 2-methylpropene. due to their hydrogen bond formation with water
molecules.
pl

pl

pl
ax

ax
The solubility decreases with increase in the number of

ax
CH,
carbon atoms.
tm

m
CHC-Br+Na-0-CH CH=CH +NaBr+ CH,OH
ct

ct
CH CH,
e

e
sp

sp

sp
2-methylpropene
R-Q***fh
re

re

re
H
@

@
Itis because alkoxides are not only nucleophiles but also strong
bases as well. They react with alkyl halides leading to elimination
reaction. Phenols are also converted to ethers by this method. REACTIONS OF ETHERS
1.Cleavage of C-O bond in ethers
ONa Ethers are least reactive of the fiunctional groups. The cleavage
ÖH
-R ofC-O bond in ethers takes place under drastic conditons with
5

5
Na x
us

us

us
excess of hydrogen halides. The reaction of dialkyl ether given
+NaOH
two alkyl halide molecules.
pl

pl

pl
ax

ax

ax
R-0-R+2HX> 2RX+H,O
tm

tm

tm
Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the
Note: Aryl, vinyl, tertiary, secondary halides can not used in this more stable aryl-oxygen bond. The reaction yields phenol and
ec

ec

reaction. alkyl halide.

sp

sp

sp
Example 14: For the preparation of an isole OH
-R
re

re

re
@

@
-0-CH), JH-X +R-X
which one is preferable reaction and why? Ethers with two different alkyl groups are also cleaved in the
same manner.

O' Na' +X -
CH, CH-0-C,H, +Hl>CH,I+C,H,OH
5

5
us

us

us

CH, CH
pl

pl

pl

CH-0-CH+Hl CH,I+CH-OH
CH
ax

ax

ax

O-x x+Na'O-CH, CH
tm

tm

tm

The order of reactivity of hydrogen halides is as follows: HI>

HBr> HCI.
ec

ec

Ans

. In the cleavage of mixed ethers with two different alkyl groups,

sp

sp

sp

By heating alkyl halide with dry silver oxide the alcohol and alkyl iodide that form depend on the nature of
(only for simple ethers):
re

re

re

alkyl groups. When primary or secondary alkyl groups are

@

present, it is the lower alkyl group that forms alkyl iodide.

CaHsl+ Ag20 +IC2Hs >CzH5OC2Hs +2Agl
Dry MECHANISM
Kemember that reaction of alkyl halides with moist silver oxide
The reaction of an ether with concentrated HI starts with
Ag,0+2H,0 = 2AgOH) gives alcohols protonation of ether molecule,
CHI +Ag,O (moist) >C,H,OH +Agl
ALCOHOLS, PAENOLS 127)-
5

AND ETHER -
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 17 of 37
t

ct

ct
pe

pe

p
Step-1:. Hydrolysis:
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
CaHs-O-CaHs +H,O 02C,H;OH

@
CH-9-CH,CH, +H-1CH,--CH,CH, + Ethyl alcohol

The reaction takes place with HBr or HI because these reagents The hydrolysis may also be effccted by boiling the ether with
are sufficiently acidic. water or by treating it with steam.
Step-2 Note: Ethers can never be hydrolysed in alkaline medium.
lodide is a good nucleophile. It attacks the least substituted
TRAIN YOUR BRAIN
5

5
carbon of the oxonium ion formed in step 1 and displaces an
us

us

us
alcohol molecule by S2 mechanism. Thus, in the cleavage of
Example 15: What will be final products?
pl

pl

pl
mixed ethers with two different alkyl groups, the alcohol and
ax

ax

ax
alkyl iodide formed, depend on the nature of alkyl groups. When

oO -0-CH, + HI
tm

m
primary or secondary alkyl groups are present, it is the lower
ct

ct
alkyl group that forms alkyl iodide (S 2 reaction).
e

e
sp

sp

sp
+CH,--CH,CH,>|1-CH,--CHcHCH,-1+ CH,CH-OH
Tansition state CH
re

re

re
When HI is in excess and the reaction is carried out at high Gi) CH- C-0-CH + HIA
@

@
temperature, ethanol reacts with another molecule of HI and is
CH,
converted to ethyliodide.
Step-3:
(ii) CHCH-0-CH,+HI A
CHCH--H +H-12CH,CH,-'H+T
5

5
OH +CH,I
us

us

us
-
Sol. (S2)
CH
pl

pl

pl
T+CH,OH,CH,CH,I+H,0
ax

ax

ax
Gi) CHOH+(CH),C-1
When one of the alkyl groups is a tertiary group, the halide
tm

tm

(Gii)
tm
CHCHOH +CHI
formed is a tertiary halide. It is because the attack by iodide
ec

ec

takes place at that carbon of the alkyl group which hasa greater
sp

sp

sp
electron pushing inductive effect and a lower electron density Example 16: Predict final product in the reactions.
(SI reaction).
re

re

re
CH CH
CH-O-CH, HX
CH,=CH2CH-0-CH,
@

@
CH CH
CH,--0-CH, +HI>CH,OH +CH,-C-1
CH CH
BF
In case of anisole, methylphenyl oxonium ion, is formed by
5

protonation of ether. The bond between O-CH, is weaker than

us

us

us

the bond between 0-C,H, because the carbon of phenyl group Example 17: CH,CH, Cl+ Ag,O-
A, Product. Product
pl

pl

pl

is sp hybridised and there is a partial double bond character. formed in the reaction is
ax

ax

ax

Therefore the attack by I ion breaks 0-CH, bond to form CH,I. (a) CHCH-0-CHCH,
tm

tm

tm

Phenols do not react further to give halides because the sp? (6) CHCHCI + AgCI
hybridised carbon of phenol cannot undergo nucleophilic
ec

ec

substitution reaction needed for conversion to the halide. (c) CHCH,-OH +AgC

-
sp

sp

sp

(d) (CHCH,-0),Ag
:CH HCH
re

re

re

OH Sol. (c) CHCH,-OH+AgC

--c
@

Example 18: Williamson's synthesis involves

(a) SI mechanism
(b)S2 mechanism
In ethers if one alky! group are benzyl, Allyl and tertiary the (c)Nucleophilic addition (d) Electrophilic addition
cleavage of ether will take place by S,I mechanism. Sol. (6) S,2 mechanism
5

128 -FULL CoURSE STUDY MATERIALJEE-XIL |

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 18 of 37
t

ct

ct
pe

pe

p
FOR
2. Electrophilic LAKSHYA in alkylJEE 2023 FREE : CLICK ME

s
substitution aryl ethers Example 19: OCH, group is

re

re

re
The alkoxy group (-OR) is ortho. para directing and activates
(a) Stronger+Rgroup than OH

@
the aromatic ring towards electrophilic substitution in the same
way as in phenol. (6) Weaker +R group than-OH
(c) Stronger +Igroup than-OH

9R RR
o-aap- R (d) Inert group
Ans. (6) Weaker +R group than-OH
(ii) Sulphonation:
5

5
us

us

us
I IV V
pl

pl

pl
OCH OCH OCH
ax

ax

ax
()Halogenation: Phenyl alkyl ethers undergo usual halogenation
in the benezene ring, e.g., anisole undergoes bromination with
SOH
(O)-(O
tm

m
bromine in ethanoic acid even in absence of iron (III) bromide
ct

ct
catalyst. It is due to the activation of benzene ring by the methoxy
e

e
sp

sp

sp
group. Para isomer is obtained in 90% yield.
sO,H
re

re

re
OCH, OCH, OCH, Anisole p-Methoxybenzene o-Methoxybenzene
sulphonic acid
@

@
sulphonic acid

O (major) (minor)

3r
(iv) Nitration: Anisole reacts with a mixture of conc. H,SO, and
Anisole 2-Bromoanisole 4-Bromoanisole
cone. HNO, to yield a mixture of ortho and para nitroanisole.
5

5
OCH
us

us

us
OCH, OCH, pCH OCH, OCH
Br NO,
pl

pl

pl
Brin H,SO
+
ax

ax

ax
Ethanoic acid HNO
tm

tm

tm
Anisole NO
Br.
ec

ec

p-Bromoanisole o-Bromoanisole Anisole 2-nitro anisole 4-nitro anisole

sp

sp

sp
(Maja) (minor) (minor) (major)
re

re

re
(i) Friedel Crafts reaction:Anisole undergoes Friedel Crafts Example 20:
@

@
reaction i.e., the alkyl and acyl groups are introduced at ortho
and para positions by reaction with alkyl halide and
acyl halide

in presence of aluminium trichloride (a Lewis acid) as

OCH,
catalyst. O
Product ofthe reaction is
-Cl
heat Product.
5

OCH, OCH
us

us

us

Anhydrous CH,
+CH,CI-AlCl
pl

pl

pl
ax

ax

ax

CH,
2-methoxytoluene 4-methoxytoluene
tm

tm

tm

(minor) (major) -OH

(
ec

ec

OCH,
QCH OCH,
sp

sp

sp

Anhydrous COCH,
re

re

re

+CHCOCI AlCl
@

Ethanoyl 2-methoxy cOCH,

Chloride acetophenone 4-methoxy (d) No reaction
(minor) acetophenone
(major) Ans: ()

1129
5

ALCOHOLS, PHENOLS AND ETHER -

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 19 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
SOMEcOMERCIALLY IMPORTANT

re

re

re
Glucose and fructose undergo fermentation in presence
of another enzyme, zymase, which is found in yeast. In

COMPOUNDS
1. Methanol: Methanol, CH,OH, can be produced by
destructive distillation of wood. Today, most of the
methanol is produced by catalytic hydrogenation of
carbon monoxide at high pressure and temperature and
5
@
wine making, grapes are the source of sugars and yeast.
As grapes ripen, the quantity of sugar increases and yeast
grows on the outer skin. When grapes are crushed, sugar
and the enzyme come in contact and fermentation starts.

5
in presence of ZnO- Cr,0, catalyst. Fermentation takes place in anaerobic conditions i.e. in
us

us

us
absence of air. Carbon dioxide is released during
pl

pl

pl
CO+2H,0 CH,OH
ax

ax

ax
fermentation.
Methanol is a colourless liquid with bp 337 K. It is highly
tm

m
poisonous in nature. Ingestion of even small quantities
CgHyOZymase2C,H,OH +2C02
ct

ct
e

e
of methanol can cause blindness and large quantities, The action of zymase in inhibited once the percentage of
sp

sp

sp
even death. Methanol is used as a solvent in paints, alcohol formed exceeds 14%. Ifair gets into fermentation
re

re

re
vamishes and chiefly for making formaldehyde, which in mixture, the oxygen of. air oxidises ethanol to ethanoic
@

turn is used as a preservative for biological specimen and
for making synthetic resins.
2. Ethanol: Ethanol, CH,OH, is obtained commercially by
fermentation.
) Fermentation: Fermentation is the oldest method of
5
@
acid which in turn makes it sour.
Distillation of a solution of ethanol and water produces
an azcotrope containing 95% ethanol and 5% water. Pure
ethanol is obtained by membrane technology.
Ethanol is a colourless liquid with bp 351 K. It is used as

5
us

us

us
making ethanol from sugars. The sugars in molasses, a solvent in paint industry and in the preparation of a

sugarcane or fruits such as grapes or starch obtained

pl

pl

pl
number of carbon compounds. The commercial alcohol is
ax

ax

ax
from various grains is converted to glucose and made unfit for drinking by mixing in it some copper
fructose, (both of which have the formula C,H,0),
tm

tm

tm
sulphate (to give it a colour) and pyridine (a foul smelling
in presence of an enzyme invertase. liquid). It is known as denaturation of alcohol. Nowadays,
ec

ec

large quantities of ethanol are obtained by the hydration

CH0+H,0ven
sp

sp

sp
CGH,0, +CH206
612 of ethene.
re

re

re
Glu co Fructose
@

@
5

5
us

us

us
pl

pl

pl
ax

ax

ax
tm

tm

tm
ec

ec
sp

sp

sp
re

re

re
@

160 FuLL COURSE STUDY MATERIAL. JEE-XII

5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 20 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
Topicwise Questions

@
ALCOHOLS AND ETHERS 9. What is formed when glycerol reacts with HI in excess

Introduction, Preparation of Alcohol & Physical CH,OH CH

(ai) CHI
5

5
properties
us

us

us
CHOH CH
1. Propene, CH -CH = CH2 can bc converted to
pl

pl

pl
1-propanol by oxidation. Which set of reagents among CH
ax

ax

ax
the following is ideal to effect the conversion CHOH
(c) H-1
tm

m
(a) Alkalinc KMnO
(d) C= O
CHs
ct

ct
(6) BH, and alkaline H,O2 CH
e

e
sp

sp

sp
10. Which alcohol produces turbidity with Lucas reagent most
(c)O,/Zn dust slowly?
re

re

re
(c) OsO1CH4,Cl2 (a) 2-Butanol (6) tButyl alcohol
@

@
2. Which of the following statemcnts is correct (c)Isobutyl alcohol (d) Diphenylcarbinol
(a) Phenol is less acidic than ethyl alcohol 11. Which of the following alcohols gives a red colour in Victor
(6) Phenol is more acidic than ethyl alcohol Meyer test?
(c) Phenol is more acidic than carboxylic acid (a) n-Propyl alcohol
(d) Phenol is more acidic than carbonic acid (6) Isopropyl alcohol
(c) (CH)c-OH
3. Boiling point of alcohol is comparatively higher than that
5

5
(d)sec. Butyl alcohol
us

us

us
corresponding alkanc duc to
12. The compound A, Band C in the reaction sequence
()Intermolecularhydrogen bonding
pl

pl

pl
PBt ale
(6) Intramolecular hydrogen bonding CH CH,OH A- KOHB C are
ax

ax

ax
(c) Volatile nature given by the set
tm

tm

tm
(d) None of these (a) CHBr, CH,CH,OH, CH,CHBr.
(b) C^HLBr, CH=CH, CH=CHBr
ec

ec
4. Which of the following compound is most acidic
(c) CH,Br, CH,=CH,, CH,Br-CH,Br
(6) CH
sp

sp

sp
(a) CH (d) CHBr, CH,CH,OH, BrCH,-CHBr
()CH CH (c) CH,OtH
re

re

re
13. The compound which docs not react with sodium is?
5. Which of the following alkanols is most soluble in water (a) C,H,OH (b) CH-O-CH
@

@
(a) 1-Butanol (b) 2-Butanol (c) CH,COOH (d)CH CHOH-CH.
14. Which of the following is not true in case of reaction
()Isobutylalcohol tyl ol
with heated copper at 300°C?
6. Dehydration of ethanol gives
(a) Phenol-> Benzyl alcohol
(a) Acetic acid (b) Ethane
(6) Primary alcohol-> Aldchyde
()Ethylene (c) Acetylene
() Secondary alcohol-> Ketonc
5

7. The alcohol which easily reacts with conc. HCl is (d) Tertiary alcohol > Olefin
us

us

us

(a) CH-CHOH-CHa -CH 15. Which of the following is the most suitable method for
pl

pl

pl

(6) (CH,)3 -C-OH removing the traces of water from ethanol?

ax

ax

ax

(a) Heating with Na metal

() CH-CH-CH-CH-OH
tm

tm

tm

(b) Passing dry HCI through it

() (CH)- CH-CHOH (c) Distilling it
ec

ec

8. In the sequence of the following reactions

() Reacting with Mg
sp

sp

sp

CH,OH CH,IKCN
Miscellaneous
re

re

re

CH,CNectionXNO Y
16. Ethanol on heating with acetic ncid in the presence of a few
@

Xand Y are respectively drops of sulphuric acid gives the smell of

() CH,CH,NH, and CH,CH,OH (a) Oil of wintergreen
6) CH,CH,NH and CH,coOH (b) Oil ofnmustard
(c) An ester
)CH,CH,OH and CH,CHO
() CH,OCH, and CH,CHO
()Oil of bitter almonds
-
5

ALcOHOLS, PHENOLS AND ETHER (131)-

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 21 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
PHENOL N;C

re

re

re
26. HO

@
lntroduction, Preparation of Physical propertles of
Phenol
17. Phenol is less acidic than
(a) Acetic acid (6) p-nitrophenol
-No-o
(c)Both (a) and (b) (c)None of these
5

5
18. The strongest acid among the following aromatic
us

us

us
compounds is ()
(a) ortho-nitrophenol
pl

pl

pl
ax

(6) para-chlorophenol

ax

ax
OH
()para-nitrophenol
tm

m
(d)meta-nitrophenol Miscellaneous
ct

ct
19. Which compound has hydrogen bonding?
e

e
(a) Toluene 27. Liebermann's test is answered by
sp

sp

sp
(6) Phenol
(c) Chlorobenzene (a) Aniline
(d) Nitrobenzene
re

re

re
(b) Methylamine
20. Which of the following compounds does not show
@

@
phenolic properties? Ethyl benzoate
(d) Phenol

(a) ETHER

Introduction, Preparation &t Physical properties of

a
GH O Ether
5

5
us

us

us
28. Williamson's synthesis is used to prepare
21. Which of the following compounds shows intramolecular
pl

pl

pl
(a) Acetone (b) Diethyl ether
hydrogen bonding?
ax

ax

ax
()PVC ()Bakelite
(a)p-Nitrophenol (6) Ethanol
29. In Williamson's synthesis, ethoxyethane is prepared by
tm

tm

Methanamine
tm
(co-Nitrophenol (d)
a) Passing ethanol over heated alumina
ec

ec

Chemical reaction of Phenol

(6) Sodium ethoxide with ethyl bromide
sp

sp

sp
22. Diazo-coupling is useful to prepare some
(c)Ethyl alcohol with sulphuric acid
re

re

re
(a) Pesticides (b) Proteins
(c) Ethyl iodide and dry silver oxide
@

@
(c) Dyes ()Vitamins
30. In which case methyl-t-butyl ether is formed?
23. Electrophilic substitution reaction in phenol take place at
(a) p-position (6) m-position () (C,H,),cONa +CH,C
(c)0-position (d) o- and p-position (6) (CH,),CONa+CH,C1

OH OH (c)(CH,),cONa+C,H,CI
(O
5

+HCI + HCNAnhydrous
24.
us

us

us

(c) CH,ÖNa +(CH),C-Ci

CHO
31. Methylphenyl ether can be obtained by reacting
pl

pl

pl

is known
ax

ax

ax

(a) Phenolate ions and methyl iodide

(a)Perkin reaction (6) Methoxide ions and bromobenzene
tm

tm

tm

(6) Gattermann reaction (c) Mcthanol and phenol

(c)Kolbereaction
ec

ec

(d)Bromobenzene and methyl bromide

(d) Gattermann-Koch reaction
sp

sp

sp

32. Conc. H,SO, heated with excess of C2H,OH at 140°C

25. Phenol reacts with CCI, in presence of aqueous alkali and to form
re

re

re

forms a product which on hydrolysis gives (a) CHCH2-O-CH3

@

(a) Salicylaldehyde
(b) Salicylic acid
(6) CH,CH2-0-CHCH
c)Benzaldehyde () CH- 0-CH2-CH2 - CH3
(d) Benzoic acid (c) CH2 = CH2

-FULL CoURSE STUDY MATERIAL JEE-XII

5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 22 of 37
t

ct

ct
pe

pe

p
33. EpoxidesFOR
are LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
( Cyclic ethers
40. The ether

@
(6) Not ethers
)Aryl-alkyl ethers when treated with HI produces
(d)Ethers with another functional group

-
34. Theprcparation of ethers from alcohols by using sulphuric
acid is called: -CH (0)-CHOH
5

5
(a) Williamson's ether Synthesis
us

us

us
(6)Williamson's continuous etherification process
_-OH
pl

pl

pl
(CZiesel'smethod
ax

ax

ax
4) Zerewitinoff method 41. The products formed in the following reaction
tm

m
35. The reaction of cthyl iodide with sodium ethoxide is
CsHs-0-CH +HI nea arc
ct

ct
(a) An electrophilic substitution reaction
e

e
(6) Amucleophilic addition reaction and CH - OH
sp

sp

sp
(a) CgH-I
() Anucleophilic substitution reaction
re

re

re
(d) A freeradical substitution reaction (6) CHs-OH and CH -I
@

@
36. The Williamson synthesis involves:
(a) Anucleophilic addition
() CsHs- CH and HO1
(b) An electrophilic substitution (d) CH and CH,O
c)SN displacement
42. Dimethyl ether when heated with excess HI gives:
(d) SN' displacement
5

5
(a)CHl and CH,OH
us

us

us
37. In the Williamson synthesis of ethers given by the general
() CHI and H,o
pl

pl

pl
equation
(c)CH+ CHI and CH,OH
ax

ax

ax
RX+R'ONa .
R-0-R' the yield from R-X (d) CHl and HCHO
tm

tm

tm
follows the sequence Miscellaneous
ec

ec

(a) CH> 1*>2°> 3° 43. The structure of the compounds formed by the reaction of
sp

sp

sp
(6) CH 1°<2°<3° diethyl ether with oxygen of air is:
re

re

re
(c) CH,1° <2°>3°. (a) CH,CH-0-0-CHCH
@

@
(d) CH> 1°<2°<3°
38. Ethyl chloride is converted into diethyl ether by (b) aHaH-O- 0-0-H

(a)Wurtzsynthesis (c)CHCH-0-0-CH-0-CH
(6) Grignard reaction (d) CHOCH)-CH0-CH
5

(CPerkin'sreaction
us

us

us

H,ONa
44. In the rection sequence A-5r B
(d) Williamson's synthesis
pl

pl

pl

Ethoxyethane, A and B are:

ax

ax

ax

Chemical reaction of Ether

() CH. CH,Br
tm

tm

tm

39. In the following reaction 'A'is (6) CH, CH,Br

0A
ec

ec

CaH5MgBr + H,C-CH2
(o)CH-CH,C,H,Br
sp

sp

sp

(c)CH=CHCH,-CHBr
re

re

re

45. Phenol and ethanol are distinguished by the reaction with

()CaH,CH,CHO
@

(a) Red litmus

(6) C2H,CH,CH,OH (6) NaHCO3

()CaHsCH,OH ()FeCl
() NaOH
()CaHCHO
5

ALcOHOLS, PHENOLS AND ETHER-

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 23 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
Learning Plus

@
1. Which ofthe following has the lowest solubility in water? 10. Ether bottles should not be kept open in air because
(a) Ether is an anacsthetic
(b) Ether forms an explosive peroxide
(a) CHCHCHCHOH (6) CH-CHcH,OH
()Ether is costly
5

5
us

us

us
(c)HOHLC-CILOH (d)CHCHcLOI (d) Ether gets oxidised to ethanol
2. Which of the follwing has the highest valuc of pK,? 11. Unsymmetrical ethers are best prepared by-
pl

pl

pl
(o) CH-CHOH )Willamson's continuous etheri fication process
ax

ax

ax
(b) (b) Rcacting Grignard reagent with alkyl halide
Cl-CH-CHOH
tm

m
e) Treating sodium alkoxides with alkyl bromides
)FC-CH-OH
ct

ct
(d) Heating an alkanol with conc. H,SO,
e

e
(d) CH-CH-CH,OH
sp

sp

sp
12. Which is mismatched-
CH (a) CH-O-CH,Four primary carbon atoms
re

re

re
(b) CH-CH-CH(OH)CH, Optically active
@

@
3. Which of the following has the highest boiling point?
() CH-0-CH (CH), Two secondary carbon atoms
(a) CH-CH-CH-CH, ()Ether is heated with CH,COCI in presence of AICI,
OH to give CHcooc.H, +CHCI
13. The compound which reacts faster with Lucas reagent at
(6) CHCH-CH-CHOH room temperature is
)CH-CH-CH,OH
5

5
(a) diethyl ether-1-ol
us

us

us
CH (6) diethyl ether-2-ol
pl

pl

pl
() 2-methyl propan-1-ol
CH
ax

ax

ax
(c) 2-methyl propan-2-ol
14. Which of the following reactions of an alcohol does
tm

tm

tm
(d CH-C--OH not involve O H bond breaking:
-
ec

ec

(a) Reaction with alkali metals

CH3
sp

sp

sp
(6) Reaction with an acyl chloride
4. Wood spirit contains
re

re

re
(c) Reaction with sulphonyl chloride
(a)onlymethanol (d)Reaction with cone. sulphuric acid.
@

@
(6) only ethanol 15. Alkyl chloride is formed when alcohol is treated with
(c) methanol + cthanol HCI in presence of anhydrous ZnCl,. The order of
(d) amixture ofa number of alcohols reactivity with respect to alcohol is:
5. Acetaldehyde reacts with CH,MgBr. The compound (a) 3°> 2°> 1° (6) 1°> 2°> 3°
formed will be
() 2> 1°> 30 () 1°>3°> 2°
5

(a) CHCH,OH (b) CHCHOHCH,

16. Methyl alcohol reacts with phosphorus trichloride to
us

us

us

()CHCH,CH,OH () Nonc of these form-

pl

pl

pl

6. Action of nitrous acid on ethyl aminc gives-

a) Methane (6) Methyl chloride
ax

ax

ax

(a) CH (b) CHOH

(c) NH ) Nitromcthane ()Acetyl chloride () Dimethyl ether
tm

tm

tm

7. Hydrogen bonuing is possible in- 17. The-OH group of methyl alcohol cannot be replaced by
chlorine by the action of
ec

ec

()Ethers (b) Hydrocarbons

c) Alcohols (a) Chlorine
sp

sp

sp

()Alkanes
8. Diethyl ether acts as a- (b) Hydrogen chloridec
re

re

re

(c) Phosphorus trichloride

()Lewisacid (6) Lewis base
@

(c)Reducingagent (d) Oxidising agent ) Phosphorus pentachloride

9. Ethers like alcohols do not form strong.. bonding. 18. Recaction of alcohol does not
show cleavage of R-O
Hence they are more volatile- linkagc
(a) Covalent (b) Hydrogen (a) ROH+ PCI, (6) ROH+SOCL,
c) Coordinate (d) None of the above (c)ROH+HCI () ROH + Na
5

(134)
us

us

us

-
FULL CoURSE STUDY MATERIAL JEE-XIL
pl

pl

pl
ax

ax

ax
m

m
 Page 24 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
19. Which of the following is produced when an aqueous

re

re

re
29. The product of the reaction of benzene with oxygen in
solution ofbutan-2-ol is refluxed with dilute acidic KMnO2

@
the presence of V,O, as catalyst at 200°C is-
)butanol (6) butanoic acid
(a)Malcic anhydride (b) Benzoic acid
potassium butanoate () butanone
. Phenol )None of these
30. Phenol with Hinsberg's reagent gives-
CH-OH
xHIO4 a) Sulphone (6) Sulphanilic acid
C=O Sulphonic ester (d)Sulphonal
20.
5

5
CH-OH 31. Kolbe's reaction consists in obtaining-
us

us

us
a) Anisol from phenol
pl

pl

pl
CH-OH (6) Salicylaldehyde from phenol and CHl
ax

ax

ax
x is moles of HIO, consumed
(c)Salicylicacid from sodium phenate and CO2
tm

m
(c) Salicylic acid from phenol and C0
(a)x=3 (6) x=2
ct

ct
32. Phenol is converted into salicylaldehyde by-
()x=4 )x=1
e

e
(a) Etard reaction
21. The hydroboration oxidation of 2-methyl propene yields-
sp

sp

sp
(6) Kolbe reaction
(a) 1° alcohol (6) 2° alcohol
re

re

re
(c) Reimer-Tiemann reaction
(c)3° alcohol (d) None
(d) Cannizzaro reaction
@

@
22. Which alcohol does not give a ketone on oxidation?
(a) Isopropyl alcohol 33. Observe the following reaction, and sclect the correct
(6) Allyl alcohol option
(c)Ethylmethylcarbinol
OH
() Methylphenylcarbinol
23. Tertiary alcohols are resistant to oxidation because: dil. HNOL+(Y)
O
5

5
(a) They do not have a hydrogen atom
us

us

us
(6) Of large +1 effect of alkyl groups
pl

pl

pl
()Of greater steric hindrance Steam distillation (Y) low boiling fraction Y is:
ax

ax

ax
(d)All the above
tm

tm

24. In phenols
tm
(a)OH group is attached in side chain OH QH
ec

ec

(6) -OH group is directly attached to benzene nucleus NO NO,

oJ
sp

sp

sp
()Both (a) & (b) (6)
() None NO
re

re

re
25. Which of the following is not a phenolic compound? NO
@

@
(a)Salol (b) o-Cresol
()Anisole () Quinol
sequence
26. What are the final products of the following OH OH
of reactions?
NO,
CH+CH,CH =CH,-AnhyACh
O
5

O,/130 C ?
us

us

us

Catalyst NO
pl

pl

pl

(a) Cumene and phenol

ax

ax

ax

(6) Phenol and acetone Zn

acetone
NaOH
34.BCH,COCI DistillationA
)Cumene and
tm

tm

tm

(d) Benzoic acid and ethane

The compounds A and B in the above reaction sequence
ec

ec

27. Phenol is obtained in large scale from

which fraction of
are
sp

sp

sp

coal-tar? a)benzcne, methyl benzoate

(b) Green oil fraction
() Light oil fraction (6) benzene, phenyl acetate
re

re

re

(d) Middle oil fraction

)Pitch C)phenyl acetate, benzene
@

28. The compound obtained by

heating cumene-
(d) benzene, phenylacetyl chloride
hydroperoxide with dil. H,SO4 is 35. Which of the following does not give cffervescence with
(a) Phenol NaHCO,?
(6) Isopropyl benzene a) Phenol (6) p-Nitrophenol
() Benzene sulphonic acid ) 2,4-dinitrophenol ()2,4,6-trinitrophenol
() None of these
5

5
us

us

us

ALcOHOLS, PAENOLS AND ETHER-

pl

pl

pl
ax

ax

ax
m

m
 Page 25 of 37
t

ct

ct
pe

pe

p
FORwhich
LAKSHYA JEE 2023 FREE : CLICK ME

s
36. The compound does not react with bromine easily 40. Ether does not form oxonium salt on reaction with.

re

re

re
at room temperature is: (o) Cold conc. H,SO,

@
a) phenol (6) 2-butyne (6) Cold conc. HCI
(c)chlorobenzene () 1-pentene () Conc. HI
37. p-Nitrophenol is stronger acid than phenol because nitro (d) None of the above
gToup is-
41. The ordinary alkyl cthers are cleaved by-
(Electron withdrawing
(a) Ethanol (b) Ethyl halide
(6) Electron donating
5

5
()BF, ()Hydrogeniodide
us

us

us
(c)Basic
42. The decomposition of cthers byHI or HBr is called.
d) Acidie
pl

pl

pl
38. In the following compounds, (a) Zerewitinoff's reaction
ax

ax

ax
OH OH OH (6) Ziesel's method
tm

m
OH (c)Williamson's method
ct

ct
() Hell-Volhard-Zelinsky reaction
NO
e

e
43. In the Williamson's synthesis for diethyl ether, which
sp

sp

sp
CH, NO,
species works as a nucleophile
re

re

re
II IV (6) Ethoxide ion
The order of acidity is: (a) Halide ion
@

@
(c) Ethyde ion (d) Hydride ion
(a) Il>V>I>I (b) I>V>Il >II
(c) I>1>l>v ()IV>1>1>I1 44. For making (CH,),C-0-C.H, the ideal combination is-
39. Intermcdiate produced during reimer tiemann's formlylation (a) (CH,),CONa and CH,Br
will be (6) (CH,),CBr and C.H,ONa
(a) CC (6) :CH, (c) Both the above
5

5
(a) None of these
us

us

us
(c)CCl (d) CHCI,
pl

pl

pl
ax

ax

ax
tm

tm

tm
Advanced Level Multiconcept Questions
ec

ec
sp

sp

sp
re

re

re
cOMPREHENSION/STATEMENT/MATCHING/
Xis Br
@

@
MCQ (a)
1. 3-mcthyl-3-hexanol can be prepared by-
(a) CH,Mgl and 3-hexanone, followed by hydrolysis (b) Y is «
-MgBr
(6) CH, Mgl and 2-Pentanone, followd by hydrolysis
)CH,Mgl and 2-butananone, followd by hydrolysis OHCH,
() CH, Mgl and propanon, followed by hydrolysis
Zis -C-CH,
5

(c)
2. Which of the following reaction esterification?
us

us

us

(a) EtOH+ Acctic anhydride- H

pl

pl

pl

H CH,
(6) EtOH+ H,CO H
ax

ax

ax

A
(d) Zis -C-CH,
tm

tm

tm

A O-HH
4. Which of the following alcohol can not be oxidized by
ec

ec

(c)EtOH+CH-C-CI KMnO,?
sp

sp

sp

)None OH
Mg/Et,O OH
re

re

re

PBr (X) (Y) )

3.
-OH
@

CH OH
(i) CH,-CH-CHO OH
(Z)
(ii) H,o
5

136 FULL CoURSE STUDY MATERIAL JEE-XU

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 26 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
5

re

re

re
Which one of the following alcohols can be oxidised by
10. Identify the intermediates of the following reaction.
KCrO,?

@
(a) Ethanol QH OH
(6) Tert butyl alcohol CHO
()Isopropyl alcohol +CHCL+NaOHA
() Allyl alcohol
6. HBO, oxymercuration-demercuration and acid catalysed
5

5
hydration will not give same product in
us

us

us
»
pl

pl

pl
CHC
(a)
ax

ax

ax
()
tm

m
ct

ct
()
e

e
sp

sp

sp
7. Compound which gives alcohol on reduction is/are (When
H
re

re

re
reacts with LiAIH) CCl,
CHCI
@

@
(a) Me-C-CI (b) Me-C -NH,

OH

(c)Me-CH-CH a)Me--oc-Me 11.

| ) CHCltNaoH, (P>Q)%yield
5

5
(i) H
us

us

us
Select the correct options:
pl

pl

pl
8. Which offollowing compound undergo acidic hydrolysis? (a) Boiling point, (P> Q
ax

ax

ax
O (b) Melting point, (Q>P)
tm

tm

tm
(c)Water solubility, (P<Q
(a) CH-CN (6) CH-E0-Et (d) Acid Strength, (Q<P)
ec

ec

12. Which of the following reaction is/are correct?

sp

sp

sp
OH OH
(CH-Ca CH-C-o--cH,
re

re

re
(c) COOH
O
@

@
NaOH
9.
(o)Oco (i) HO

CH,-CH-CH, CH-CCNa'()CHl, Y) HrdBaSO4, (Z) OH

Identify X, Y, Z:
5

5
us

us

us

(a) Yis CH-CH-CH2C = CCH CoOH

pl

pl

pl

6-CH QH OH
ax

ax

ax

CHO
tm

tm

tm

(6) Yis CH-CH,-CHC= CCH3 NaOH

(i)H,O
tcH
ec

ec
sp

sp

sp

C)Zis CH-CH-CH2 -CH-CH-CH,

re

re

re
@

6-CH3

(d) Xis CH-CHCH2C = CCH3 CHO

5

ALcOHOLS, PHENOLS AND ETHER

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 27 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
15. The products of following sequence of reactions are

re

re

re
,
NO

@
FSn/HC GNaNO, /HCI
BrFe A
Pyridine
CH-G-C
O]+ H,O& I
NO, OH
OH OH
5

5
us

us

us
+HCHONaOH O OH+ )H= (6) 1-
pl

pl

pl
Br
ax

ax

ax
NH, NO
tm

m
OH

-O
ct

ct
o-O
e

e
sp

sp

sp
Br
16. Coupling reaction takes place when benzene diazonium
re

re

re
chloride is treated with
@

@
CH,OH
(a) Benzaldehyde
13. Which of the following can show positive bromine water (6) a-naphthol
test?
e) N,N-dimethyl aniline
OH OH
() Phenol
(a)
5

5
Comprehansion-1 (No. 17 to 19)
us

us

us
Aldehydes and ketones react with one molecule of an
OH
H
pl

pl

pl
alcohol to form compounds called hemiacetals, in which
SOJH COOH
ax

ax

ax
there is one hydroxyl group and one ether-like group.
Reaction ofa hemiacetal with a second molecule ofalcohol
tm

tm

tm
gives an acetal and a molecule of water. We study this
14. Which of the following reaction is/are correct?
ec

ec
reaction
CI
sp

sp

sp
CHCl
ROH ,OH ROH OR
re

re

re
KOH
* OR H OR
@

@
The carbonyl A hemiacetal An acetal
group of an (has an-CH and (has two-OR
CHFCl an-OR group to groups to the
aldehyde or ketone
(6) KOH the same carbon) same carbon)

Draw structural formulas for the hemicetal and acetal formed

from these reagents. The stoichiometry of each reaction is
OH given in the problem.
5

5
us

us

us

)+HCHO H'orÕH
pl

pl

pl

( A. =0+2CH,CH,OH (P)
ax

ax

ax
tm

tm

tm

Cyclohexanone Ethanol
ec

ec

HOcH-CClh

- 0+HOCH,CH,OH (R)
sp

sp

sp

B.
HO
re

re

re

Cyclohexanone Ethylene glycol

@

-CH-CCI
OH
Acetone
H'Q
OH
cis-1,2-Cyclohexanediol
5

5
us

us

us

-FULL COURSE STUDY MATERIAL JEE-XI

pl

pl

pl
ax

ax

ax
m

m
 Page 28 of 37
t

ct

ct
pe

pe

p
17. Product P is-
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
20. Here the nucleophile CH, attacks on

re

re

re
OEt (a) C (6) C
OEt

@
(d)Any of the three
a) (6)
OEt 21. Epoxides react with Grignard reagent to form
OEt ) Primary alcohols
(6) Secondary alcohols
OMe OMe () Tertiary alcohols
OPr
I a) Any of the three
5

5
us

us

us
OPr 22. On the basis of above passage, predict which of the
Product Qis-
pl

pl

pl
18. reaction is feasible?
ax

ax

ax
tm

m
(a)
D"(j) Mg, ether HCEH5
ct

ct
()
e

e
(i) CH,CH0
sp

sp

sp
(Gi) H,O
re

re

re
(6)
@

@
(i)
MgBr
G) CH,CHO -o
X (i) H,o
5

5
us

us

us
HaC CHCH3
pl

pl

pl
(ii) ) CH,CHMgBr
ax

ax

ax
(i) H,o
19. Product R is- OH OH
tm

tm

tm
ec

ec
()only (i) (6) 6) and i)
()all the three (d)none of the three
sp

sp

sp
(a) (6)
Comprehension-3 (No. 23 to 25)
re

re

re
Reimer-Tiemann reaction introduces an aldehyde group
@

@
on to the aromatic ring of phenol, ortho to the hydroxyl
group. This reaction involves electrophilic aromatic
substitution. It is a a general method for the synthesis of
substituted salicylaldehydes as depicted below:

Comprehension-2 (No. 20 to 22)

5

5
us

us

us

Grignard reagents are powerful nucleophiles and strong OH OH

bases. They act as nucleophiles by attacking a variety of
CHO aq. HCI
pl

pl

pl

CHO
compounds including saturated and unsaturated carbon
ax

ax

ax

atoms. Examples of reaction on saturated carbon include Intermediate

tm

tm

tm

oxiranes (epoxides) which form alcohols as the final CH CH CH

ec

ec

product. I II
sp

sp

sp

8-8+
R MgX + H20CH2 R-CH-CH,OH 23. Which one of the following reagents is used in the above
re

re

re

H,C
reactions?
@

Examples of reaction on unsaturated carbon are attack on

(a) aq. NaOH+CH,CI
>C=0,-C=N, >C=S etc.
R" (b) aq. NaOH +CH,CL

R
ROR"Mg
R
X- Ho R-OH )aq.
()aq.
NaOH+CHCL
NaOH+CCL
5

ALcOHOLS, PHENOLS AND ETHER

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 29 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
28. Match the column:

re

re

re
24. The electrophile in this reaction is-
ColumnI ColumnII

@
(a) CHCI (6)CHC
()CC (a) Oxidation of 1° (P) KMnOA
25. The structure of the intermediate (1) is: alcohol in aldehyde

ONa QNa
CHCI CHC (6) CrO HCI Collin's reagent
5

5
N
us

us

us
(a) (6)
pl

pl

pl
CH, CH
ax

ax

ax
Cro,2 (R) Jone's reagent
tm

m
ONa ONa
ct

ct
(d) Oxidation of alkene (S) PCC
CCh CHOH
e

e
into acid
sp

sp

sp
29. Match this List-I with List-lI and then select the answer
re

re

re
CH CH from the codes given below the lists
@

@
26. Match the column: List I List II
Column-I Column-1II

(aCH P) Reduces by LAH

(a)
HOOOH P) p-Cresol
CH,

-
6) O
5

5
(Hydroquinone
us

us

us
CHoCH Reduce by NaBH,
pl

pl

pl
ax

ax

ax
O HOH
(R) p-Benzoquinone
tm

tm

tm
CH-C-OH R Positive lodoform OH
ec

ec

( OH (S) Reacts with Na to evolve

sp

sp

sp
H gas HO-O-4, (S) Salicyl alcohol
re

re

re
27. Match the column:
@

@
Column-I Column-II1
OH
NUMERICAL VALUE BASED
(@) P) H/Ni 30. Number of compounds that can give purple colour with

-
neutral FeC,
5

OH
us

us

us

--
OH OH OCH OH
pl

pl

pl

COOH
ax

ax

ax

(b) PCC
tm

tm

tm
ec

ec

OH
CH,
sp

sp

sp

(i) (iii) (iv)

HPO/A
re

re

re
@

OH OH
Conc. HCl
(v) OH
(VI)
5

5
us

us

us

FULL CoURSE STUDY MATERIAL JEE-XU

pl

pl

pl
ax

ax

ax
m

m
 Page 30 of 37
t

ct

ct
pe

pe

p
31. How manyFOR reactions
LAKSHYAgiven below
JEE are
2023 FREEof: CLICK
examples 34. If ME

s
the starting material is labelled with deuterium as
elimination reactions?

re

re

re
indicated, predict how many total deuterium atoms will be

@
present in the major elimination product?
CH-CH=CH, CH- CH-CH3
OH HO CD

Conc. HS04
() CH-CH-Br NaOH CH-CH-OH (a A
5

5
us

us

us
KOH
( (I) CHCH-CHAlc. CH-CHCH,
pl

pl

pl
ax

ax

ax
Br
HCH
tm

m
Conc. HSO4
ct

ct
A
e

e
(V) CH-CH-CH-CH,EOHA CH-=CH-CH,
sp

sp

sp
CH,CI
re

re

re
35. In the given reaction:
@

@
Br QH
Alc. KOH
CH-CH-CH-CHCOnco Alkenes
Ph
5

5
us

us

us
CH Total number of alkenes (Including stereo isomers) formed
pl

pl

pl
will be
CH-C-CH-CH, Con. H,$0,
(v
ax

ax

ax
OH 36. Observe the following reaction sequence
tm

tm

tm
ec

ec

Con.HCI+Anhydrous ZnC, OH OH
(VIT) Ph-CH-ÇH-CH,
Ph
sp

sp

sp
OH Ph
re

re

re
@

@
Ph-ÇH-CH,-CH,
Conc.HS04.(bo)
(1)
(G) LiAIH

CH, CH
HPO
(VIm H
OH HI )
5

H (3)
us

us

us

CH
pl

pl

pl

Calculate molecular mass [W] ofproduct I and report your

ax

ax

ax

32. An alcohol (A), 0.22 gofthis alcohol liberates S6 ml CH,

of
answer as N, whereN=W+3.
tm

tm

tm

at STP on reaction with CHMgBr. Write the molecular

weight of alcohol which satisfy these conditions.
ec

ec

NO
sp

sp

sp

37. Sn/HC
NasH on
re

re

re

-CH-OH F5, (X
@

NaNO, H0, Product 2Z

HCI 0-5 C

Find the molecular weight ofZ.

The number of times S2 reaction has taken place 1S. ******
5

ALcoHOLS, PHENOLS AND ETHER-

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 31 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
JEE Mains & Advanced Past Years Questions

@
JEE-MAINN (c) A- CIl,
PREVIOUS YEAR'S
1. Which is the most suitable rengent for the following (CL,
5

5
us

us

us
transformation? (c) A- IO O B H0
YYO
pl

pl

pl
OH
ax

ax

ax
= OH
CH,-CH=CH-CH -CH-CH, -> CH, -ClH Cl-CIl,Co,II
The major produet of the following reaction is
tm

m
6.
JEE Main-2019 (January)| 10CIL,CIL,
ct

ct
(a) Tollen's reagent
e

e
(6) I,/NaOH
HSO
sp

sp

sp
(c) CrOCYCs,
()alkalineKMnO,
re

re

re
2. Heating of 2-chloro-1-phenylbutane with EtoK/ELOH JEE Main-2020 (September)
@

@
gives X as the major product. Rcaction of X with CHCH, CHCH,
Hg(OAc)/H,O followcd by NaBH, gives Y as the major
product. Y is (b)
(a)
JEE Main-2019 (April1
QH
CH CH, CHCH,
(a P (6) Ph
5

5
us

us

us
OH
() ()
pl

pl

pl
(c) Ph (d) PH
ax

ax

ax
OH
7. Which ofthe following derivatives of alcohols is unstable
tm

tm

tm
3. The synonym for water gas when used in the production
in an aqucous basc?
ofmethanol is:
ec

ec

JEE Main-2019 (April) JEE Main-2020 (September)

sp

sp

sp
(a) natural gas (b) laughing gas
() syn gas (d) fucl gas
re

re

re
4. Arrange the following compounds in increasing order of
(a)RO Me (b) RO-CMe,
@

@
C-OH bond length:
Methanol, phenol, p-ethoxyphenol
JEE Main-2020 (January)| RO
(c)
(a) methanol < phenol <p-cthoxyphenol RO O
(6) phenol < methanol <p-ethoxyphenol
(c) phenol <p-ethoxyphenol < mcthanol 8. The major product ofthe following reaction is:
(d) methanol<p-cthoxyphenol<phenol
5

OH
us

us

us

5. Among the compound A andl with molecular formula

(1)HC
AICIL(Anhyd.)
CHO, A is having higher boiling point than The
B.
pl

pl

pl
ax

ax

ax

possible structures ofA and B are:

JEE Maln-2019 (January)|
Main-2020 (January)]
tm

tm

tm

JEE
( (6) Ck
ec

ec

(a) A= H0 OH B-CH,O OCH,

Ch
sp

sp

sp

OH OCH,
re

re

re
@

(b) A= CH,O OCH, B- HO

OH
OH ot (d)
OH

OCH,
5

(142 -FuLL CoURSE STUDY MATERIALJEE-XII

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 32 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA
X showingJEE 2023 FREE : CLICK ME

s
9. An organic compound the following solubility 12. The organic compound that gives following qualitative

re

re

re
profile is-
analysis is:

@
Test Inference
Water A. Dil. HCl nsoluble
Insoluble B. NaOH solution soluble
X 5%HCI Insoluble CBr/water Decolourization
10% NaOH JEE Main-2019 (Apri)]1
Soluble
OH
5

5
NH
us

us

us
10 %NaHCO Insoluble (6)
pl

pl

pl
ax

ax

ax
JEE Main-2019 (April)I NH, OH
tm

m
a)m-Cresol (6) Olcic acid (c)
ct

ct
()0-Toluidine (d) Benzamide
e

e
10. The major product of the following reaction is: 13. The increasing order of boiling points of the following
sp

sp

sp
compounds is
H
re

re

re
OH OH OH OH OH
@

@
) aq. NaOH
(1i) CHI
JEE Main-2019 (January)]
ÇH, CH, CH NO, NH, OCH
OH OCH IV
5

5
us

us

us
JEE Main-2020 (September)]
CH (a)Il<I<I<IV
pl

pl

pl
(b) IV<1<1<|
ax

ax

ax
CH,
(c) I<II<IV<I
OH OH
tm

tm

()I<IV<II<I
tm
( 14. Themajor product formed in the following reaction is:
ec

ec

CH CH,
sp

sp

sp
C
re

re

re
11. The major product of the following reaction Heat
@

@
JEE Main-20181

HO
2)SoC,/A
(3)A
OH
HO
5

5
us

us

us

JEE Main-2019 (April01 oH

pl

pl

pl

OH OH
ax

ax

ax

O 15. 1-methyl-ethylene oxide when treated with an excess of

tm

tm

tm

HBr produces:
ec

ec

( (b) JEE Main-2020 (January)]

Br Br
CI
sp

sp

sp

HO (a)Br (6)
Br
re

re

re

CH,
@

CH, Br
(c)Br
CH
() (d)
CI HO
5

ALcOHOLS, PHENOLS AND ETHER -

us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 33 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE is:2023 FREE : CLICK
(a) ME
amine, alcohol (6) alcohol, phenol

s
16. The major product [B] in the reactions

re

re

re
CH, (c)alcohol, amine amine, phenol
19. Reaction of Grignard reagent, C,HMgBr with CHO

@
CH,-CH- CH CH-OCH, - CH, followed by hydrolysis gives compound "A" which reacis
instantly with Lucas reagent to give compound B,
The Compound B is:
CCl.
HHI
Heat
A Alcohol

JEE Main-2020
A
B]
(September)|
JEEMain-2021(March)]
(a) CH-CH-CH=CH-CH
5

5
us

us

us
CH,
- (b)
pl

pl

pl
(6) CH,-CH, = CH, (a)
CH3
ax

ax

ax
CH,
tm

m
()CH,-CH =C- CH,
ct

ct
(d) CH=CH CH3 C CH
e

e
17. Given below are two statements:
sp

sp

sp
Statement I: o-Nitrophenol is steam volatile due to
intramolecular hydrogen bonding. CH3 CH3
re

re

re
Statement II: o-Nitrophenol has high melting due to
@

hydrogen bonding.
In the light of the above statements, choose the most
appropriate answer from the options given below:
JEE Main-2021
(a) Both Statement I and Statement II are true
(6) StatementI is true but Statement II is false
5
@
20. Given below are two statements:
StatementI:2-methylbutane on oxidation with KMn0,
(February)] gives 2-methylbutan-2-ol.
Statement II: n-alkanes can be casily oxidised to
corresponding alcohols with KMnO.

5
(c)Statement I is false but Statement II is true Choose the correct option:
us

us

us
(d) Both Statement I and Statement II are false JEE Main-2021 (MarchHI
pl

pl

pl
18. Ceric ammonium nitrate and CHCI,/alc.KOH are used for (a) Both statement I and statement II are incorrect
ax

ax

ax
the identification of functional groups present in and 6) Both statement I and statement II are correct
respectively. (c) Statement I is correct but statement II is incorrect
tm

tm

tm
JEE Main-2021 (February)] )Statement I is incorrect but statement II is correct
ec

ec

JEE-ADVANCED
sp

sp

sp
PREVIOUs YEAR'S
re

re

re
1. Match the reactions in Column I with appropriate options in Column I1.
@

@
JEE-2012]
ColumnI Column III

(
a N.a- OH PC
NaOH/H,O
N-NK OH
)Racemicmixture
5

5
us

us

us

OH OH CH
pl

pl

pl

--CH, H,C
ax

ax

ax

(6) H,C CH3 Addition reaction

H,CH, CH
tm

tm

tm
ec

ec

OH
1.LiAIH
sp

sp

sp

2. H,o R) Substitution reaction

CH
re

re

re
@

HS a Base (S) Coupling reaction

(T) Carbocation intermediate
5

5
us

us

us

FULL CoURSE STUDY MATERIAL JEE-A"

pl

pl

pl
ax

ax

ax
m

m
 Page 34 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
2. The major product of the following reactionis

re

re

re
@

@
RCH,OH OH
H (anhydrous) NaOH(ag)
6. In thc rcaction /B, the
1JEE-20121
a) a hemiacetal (6) an acetal
(c)an ether ester intermediate(s) is(arc)
(an
5

5
us

us

us
3. In the following reaction sequence, the correct structure(s) JEB-2012]
ofX is (are)
pl

pl

pl
ax

ax

ax
Me
Me,0_
X PBr, 0°
tm

m
2)Nal, MeCO
(3) NaN,. HCcONMe
ct

ct
enantiomerically pure Br
e

e
JEE Advanced-20181
sp

sp

sp
(a) (6)
Me uOH Mea OH
re

re

re
(a) Br Br Br
@

@
.
Me WOH
(d)
Me OH
4. Total number of hydroxyl groups present in a molecule of
the major product P is
5

5
us

us

us
(c) ()
pl

pl

pl
Br
ax

ax

ax
(i)H,Pd-BaSO,.quinolinc Br
P
(idlil. KMn0, (excess),273K
tm

tm

tm
ec

ec

7. Amongst the following, the total number of compounds

JEE Advanced-2019]
sp

sp

sp
soluble in aqueous NaOH is
re

re

re
5. In the reaction OCH, HBr the products H,C CH COOH OCH,CH,
@

@
CH,OH
are
1JEE-2012
OA NO,
5

(a) Br OCH, and H,

us

us

us
pl

pl

pl
ax

ax

ax

OH
( Br and CH,Br
tm

tm

tm

CH,CH,
CH,CH,
ec

ec
sp

sp

sp

(9 -Br and CH,OH CH

re

re

re
@

ÇOOH

-OH and CH,Br

C JEE-20101
ALCOHOLs, PHENOLS AND ErHR- 145
5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 35 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
8. The compounds P Q and S

re

re

re
@

@
cOOH OCH

HO H,c
C S
5

5
Were separatoly subjected to nitration using HNO,/H,SO, mixture. The major product formed in ench case respectively, is
us

us

us
JEE-2012)
pl

pl

pl
ax

ax

ax
COOH OCH
tm

m
ct

ct
(HO
e

e
H,C O,N
sp

sp

sp
NO2 NO,
re

re

re
@

@
COOH OCH
(6) HO NO2 H,C NO2
NO2
5

5
us

us

us
NO,
pl

pl

pl
OCH
ax

ax

C ax
COOH
tm

tm

tm
(HO H,c NO,
ec

ec

NO2
sp

sp

sp
re

re

re
@

@
COOH OCH
NO2
()HO H,C NO
NO2
5

9. An organic compound (CH,,0)rotates plane-polarized light. It produces pink color with neutral FeCl, solution. What is the
us

us

us

total number of all the possible isomers for this compound?

pl

pl

pl

JEE (Advanced)-2020]
ax

ax

ax
tm

tm

tm
ec

ec
sp

sp

sp
re

re

re
@

-FULL COURSE STUDY MATERIAL JEE-X

5

5
us

us

us
pl

pl

pl
ax

ax

ax
m

m
 Page 36 of 37
t

ct

ct
pe

pe

p
FOR LAKSHYA JEE 2023 FREE : CLICK ME

s
re

re

re
@

@
ANSWER KEY

Topicwise Questions
1.(6) 2.(b) .(a) 4.() 5.(d) 6.(c) 7.(b) 8.(a) 9.(c) 10.(c)
5

5
us

us

us
11.() 12.(c) 13. (b) 14. (a) 15. (c) 16.() 17.() 18.(c) 19.(b) 20. (a)
pl

pl

pl
21.(c) 22.(c) 23.(() 24. (b) 25. (b) 26.0 27.(d) 28.(b) 29.(6) 30. (b)
ax

ax

ax
31.(a) 32. (b) 33.(a) 34. (b) 35. (c) 36. (c) 37. (a) 38. (d) 39. (b) 40. (a,d)
tm

m
ct

ct
41.(6) 42. (b) 43.(b) 44.(c) 45.(c)
e

e
sp

sp

sp
Learning Plus
re

re

re
1.(a) 2. (d) 3.(6) 4. (a) 5. (6) 6.(b) 7.(d) .(b) 9.(6) 10.(6)
@

@
11..(c) 12. (c) 13. () 14.(d) 15.( 16. (6) 17. (a) 18. (d) 19. () 20. (a)
21.( (a) 22. (b) 23. (a) 24.(6) 25. (c) 26. (6) 27. (d) 28. (a) 29.(() 30. (e)
31. (c) 32. (c) 33. (d) 34.( 35. (a) 36.(c) 37. () 38. (d) 39. (a) 40..(c)
41. (d) 42. (b) 43. (b) 44. (a)
5

5
us

us

us
Advanced Level Multiconcept Questions
pl

pl

pl
COMPREHENSION/STATEMENT/MATCHING/MCQ
ax

ax

ax
1. (a, b, c) 2.(a, b, c) 3. (a, b, c) 4. (b, d) 5. (a, c, d) 6.(a, b, d) 7.(a, c, d) 8.(a, b, c, d) 9.(a, c, d)
tm

tm

tm
10.(a, b) 11.(b, c) 12. (a, b, c, d) 13. (a, b, c, d) 14.(a, b, c, d) 15. (b, c, d)
ec

ec

18. (b) 19. (b) 20. (a) 21. (d) 22.( 23. () 24.(() 25. (6)
16.(b, c, a) 17. (b)
(c)Q. () P
sp

sp

sp
S; (d)>R, S 27. (a)- P; (b)-Q: (c)-R; (d)-S 28. (a)-QS, (6) S,
26. (a)-> P,Q, R; (6)-> P; («)>P,
34. [61 35. [5]
re

re

re
31. [4] 32. [88] 33. [31
29.(a) Q, (b) R, (¢) S, (d) 30. [4]
@

@
36. [78] 37. [94)

JEE Mains & Advanced Past Years Questions

JEE-MAIN
PREVIOUS YEAR'S
5

3.(c 4.(e) 5.(a) 6.() 7.(a) 8. (c) 9.(a) 10.(b)

1.(b) 2.()
us

us

us

13. (None) 14.(c) 15.(a) 16. (c) 17.( 18.(c) 19.( 20.(c)
11.(d) 12.(a)
pl

pl

pl
ax

ax

ax

JEE-ADVANCED
tm

tm

tm

PREVIOUS YEAR'S
ec

ec

2. (b) 3. (b) 4.(6.00) 5.(d) 6.(a, b,c) 7.(4) 8.(c)

1.(a)-R, S, T;(6)-T;(c)-P, Q;(d)-R
sp

sp

sp

9.(6)
re

re

re
@

147
5

ALCOHOLS, PHENOLS AND ETHER-

us

us

us
pl

pl

pl
ax

ax

ax
m

m
m tm tm tm t
ax ax ax ax
pl pl pl pl
us us us us
5 5 5 5

@ @ @ @
re re re re
sp sp sp s
ec ec e ct
pe
ct
m tm tm m
ax ax ax insTTre
ax
pl pl pl pl
us us us us
5 5 5 5

@ @ @ @
FOR LAKSHYA JEE 2023 FREE : CLICK ME

re re re re
sp sp sp s
ec ec e ct
pe
ct
m tm tm m
ax ax ax ax
RM pluss

JOIN NOW
pl pl pl pl
us us us us
5 5 5 5

@ @ @ @
re Search Doyish Sou PanTclegram re re re
Lalkhya E2023 Free
s
Page 37 of 37

sp sp sp p