Alcohols, Phenols and Ethers

Chapter 17

Alcohols, Phenols and Ethers

Chapter Contents
Introduction
 Introduction
This group of compounds reflects its importance in a large segment of
 Alcohols and Phenols :
Classification our daily utilities. Ethanol is the main component of alcoholic drink,
Glycerol which is a trihydric alcohol is used in various cosmetic
 Nomenclature
formulations. Phenols are largely used in antiseptic formulations and
 Alcohols and Phenols ethers are basic ingredient for fragrances due to their higher volatility.
 Preparation of Alcohols Interestingly, in the view of chemical bonding all these molecules have
same pattern of bonding as in water, all of them possess sp3 hybridised
 Preparation of Phenols
oxygen as central atom, this is the reason to put these different
 Some Commercially functional groups together.
Important Alcohols
 Ethers
ALCOHOLS AND PHENOLS : CLASSIFICATION
 Preparation of Ethers
Alcohols and phenols may be classified as mono, di, tri-or polyhydric
compounds depending upon number of hydroxyl groups respectively in their
structures as given below:
OH
Monohydric : CH3OH, C2H5OH,

OH
CH2OH OH
Dihydric :
CH2OH
OH
CH2OH
Trihydric : CHOH
OH
CH2OH
OH
Monohydric alcohols may be further classified according to the hybridisation
of the carbon atom to which the hydroxyl group is attached.
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188 Alcohols, Phenols and Ethers NEET
(i) Compounds Containing C  OH bond :

sp 3
(a) Primary, secondary and tertiary alcohols : In these three types of alcohols, the –OH group is
attached to 1ºC, 2ºC and 3ºC atom respectively.
CH2OH CH – OH C – OH
(1º) (2º) (3º)
(b) Allylic alcohols : In these alcohols, the –OH group is attached to a sp3 hybridized carbon next
to the carbon-carbon double bond.
H CH3
CH2 = CH – CH2 – OH CH2 = CH – C – OH CH2 = CH – C – OH
Primary CH3 CH3
Secondary Tertiary
(c) Benzylic alcohols : In these alcohols, the –OH group is attached to a benzylic carbon atom.
H CH3
CH2OH C – OH C – OH
CH3 CH3
Primary Secondary Tertiary
(ii) Compounds Containing C  OH bond : These alcohols contain –OH group bonded to a carbon-
sp 2
carbon double bond i.e., vinylic carbon or to an aryl carbon.
Ex. : Vinylic alcohol : CH2 = CH – OH
OH
Phenols :
NOMENCLATURE
(a) Alcohols : The common name of an alcohol is derived from the common name of the alkyl group and
adding the word alcohol to it.
Ex. : CH3OH : Methyl alcohol

CH3CH2OH : Ethyl alcohol
CH3 – CH – OH : Isopropyl alcohol

CH3
CH3
CH3 – C – CH2 – OH : Neopentyl alcohol
CH3
IUPAC-name of an alcohol is derived from the name of the alkane and adding suffix ‘ol’ while the letter
‘e’ of the alkane is dropped
CH3 – OH Methane + ol = Methanol
CH3CH2 – OH Ethane + ol = Ethanol
4 3 2 1
CH3  CH2  CH2  CH2  OH Butane + ol = Butan-1-ol
(n-butylalcohol)
NEET Alcohols, Phenols and Ethers 189
CH3
3 2 1
CH3 – C – CH3 2-methylpropane + ol = 2-Methylpropan-2-ol
(tert-butylalcohol)
OH
For naming of polyhydric alcohols, the ‘e’ of alkane is retained and the ending ‘ol’ is added. The number
of –OH groups is indicated by adding the multiplicative prefix, di, tri, etc. before ‘ol’.
Ex. : HO – CH2 – CH2 – OH ethane-1, 2-diol
(Ethylene glycol)
3 2 1
CH2 – CH – CH2
propane-1, 2, 3-triol
OH OH OH (Glycerol)
Cyclic alcohols are named using the prefix cyclo and considering the –OH group attached to C–1
OH
OH CH3
Cyclopentanol
2-Methylcyclopentanol
(b) Phenols : The simplest hydroxy derivative of benzene is phenol
OH CH3 CH3
OH
OH
Phenol 2-Methylphenol 3-Methylphenol
Dihydroxy benzene derivatives are named as 1, 2-, 1, 3- and 1, 4-benzenediol
OH OH OH
OH
OH
OH
(Catechol) (Resorcinol) (Hydroquinone or quinol)
Benzene-1, 2-diol Benzene-1, 3-diol Benzene-1, 4-diol
Meta trihydroxy benzene derivative is known as phlorogucinol
OH
HO OH
Structures of functional groups : In alcohols, the oxygen of –OH group is attached to carbon by a
 bond formed by the overlap of a sp3 hybridized orbital of carbon with a sp3 hybridized orbital of oxygen.
142 pm 96 pm
H 109º
O H H
H C O
108.9º
H
136 pm
The bond angle in alcohol is slightly less than the tetrahedral angle. It is due to the repulsion between
the unshared electron pairs of oxygen.
The carbon-oxygen bond length in phenol is slightly less than that in methanol. This is due to
(i) Partial double bond character
(ii) sp2 hybridised state of carbon to which oxygen is attached
ALCOHOLS AND PHENOLS

Preparation of Alcohols
1. From Alkenes :
(A) By acid reflux followed by hydrolysis : Alkenes react with water in the presence of acid as catalyst.
The addition reaction takes place in accordance of Markovnikov’s rule.
OH
(i) H2SO4
Ex. RCH CH2 RCH CH3 + RCH2CH2OH
(ii) H2O
(major) (minor)
Mechanism :
Step I : Protonation of alkene
H2O + H+  H3O+
H H H
CH3 + H H
C = CH2 + H – O – H CH3 – C – C + CH3 – C – C + H2O
H H H
H H
(Less stable) (More stable)
Step II : Nucleophilic attack of H2O on carbocation
H H
CH3 – C – CH3 + H2O CH3 – C – CH3
(more stable)
O
H H
Step III : Deprotonation to form an alcohol
H H
H +
CH3 – C – O + H2O CH3 – C – OH + H3O
H
CH3 CH3
Major product comes from more stable intermediate.

(B) By hydroboration-oxidation : Diborane reacts with alkenes to give trialkyl boranes, which is oxidised
to alcohol by H2O2 in alkaline medium to give alcohol.
(i) B2H6/TH F
RCH CH2 – RCH2 CH2 OH
(ii) H2O2/OH
Mechanism :
BH3 RCH CH2

RCH CH2 RCH – CH2 RCH2CH2BH2 (RCH2CH2)2 BH
H – BH2
-Complex
(syn addition)
–
H2O2/OH RCH = CH2
3RCH2CH2OH + B(OH)3 (RCH2CH2)3 B
(major) trialkyl borane
 Here anti-Markovnikov addition product is major product. Addition to diborane to double bond is syn
selective
 In this reaction alcohol is obtained in excellent yield.
 Less hindered double bonds can be selectively reduced by this method.
(C) Oxymercuration-Demercuration: Alkenes can be converted into alcohols by this method. Markovnikov's
addition of water takes place (without rearrangement).
CH3 C H3 HgOAc CH3
Hg(OAc) 2 NaBH 4
CH3 C CH CH2 H2O
CH3 C CH CH2 OH–
CH3 C CH CH 3
CH3 CH3 OH CH3 OH
2. From hydrolysis of alkyl halides :

Alkyl halides upon hydrolysis yields alcohol.
aq. KOH
RCH2 X (SN2) HO CH2R
1º alkyl halide 1º alcohol
R1 R2 R1 R2 R1 R2
aq. KOH
C X SN1 HO C + C OH
R3 R3 R3
3º alkyl halide (Racemic mixture)
3. From carbonyl compounds :

(A) By reduction of aldehyde and ketones : Aldehydes and ketones can be reduced to the corresponding
alcohols by using reducing agents Pd/H2, LiAIH4, NaBH4
O
[H]
R C H RCH2OH
Aldehyde 1º alcohol
R [H] R
C=O CH — OH
R Ketone R 2º alcohol
(B) By Grignard reagent : Addition of Grignard reagent to carbonyl group is the nucleophilic addition
reaction. The adduct formed upon hydrolysis yields an alcohol.
Note : If one of the aldehyde is formaldehyde then it is oxidised.
+
R1 R Mg X R1 OH
C O C
H2O
R2 R2 R
Formaldehyde gives 1° alcohol, other aldehyde give 2° alcohol and ketone gives 3° alcohol.
+
R1 R
R1 O MgX H2O R1 OH
Mechanism : C O C C + Mg (OH) X
R2 R2 R R2 R
Adduct
Here If R1 R2 H, alcohol will be RCH2 — OH (1° alcohol)
R
If R1 H or R2 H, alcohol will be CH OH (2° alcohol)
R1
R
If R1  H or R2  H, alcohol will be R1 C OH (3° alcohol)
R2
Thus by this reaction primary, secondary and tertiary alcohols can be prepared.
Note : Reactivity order of the substrates with Grignard reagent is
active-H compounds > – CHO > C = O > – COCl > – COOR > – CH2 X
(C) From carboxylic acids : Carboxylic acids are reduced to primary alcohol in excellent yield by lithium
aluminium hydride
O
(i) LiAlH4
R C OH RCH2 OH
(ii) H2O
Here reducing agents can be Pd/H2, LiAIH4 and B2H6; NaBH4 does not reduce carboxylic acids and
esters. Esters easily reduce to alcohols by use of Pd / H2.
H
R  COOR 
2
Pd
 R  CH2OH  ROH
Note : LiAlH4 is an expensive reagent and therefore used for preparing special chemicals only.
Example 1 : Give IUPAC name of the expected product in the following reactions.
LiAIH4
(i)
O
H2SO4 /(i)
(ii) major product
H2O (ii)
O
Pd/H2
(iii)
O
Solution : (i) : butan-2-ol

OH
OH
(ii) : 2-methyl butan-2-ol
(iii) OH : ethanol
Preparation of Phenols
Phenols can be prepared from benzene derivatives by any of the following methods :
1. From Haloarenes: Chlorobenzene is fused with NaOH at 623 K and 320 atmospheric pressure, phenol
is obtained by acidification of sodium phenoxide
– +
Cl ONa OH
623 K HCl
+ NaOH 300 atm
sod. phenoxide
It involves benzyne mechanism.

2. From diazonium salt :Diazonium salts are hydrolysed to phenols by warming with water or by treating
with dil.acids.
+ –
NH 2 N2Cl OH
NaNO2 H2O/
+ N2 + HCl
HCl
3. From benzenesulphonic acid : Benzene sulphonic acid is fused with NaOH. Acidification of the sodium
salt gives phenol.
SO3H O–Na+ OH
Oleum NaOH +
H /H2O

sod.phenoxide
4. From cumene : Cumene is oxidised in air to form cumene hydroperoxide. It is converted to phenol and
acetone by treating with dilute acid.
CH3 CH3 CH3 CH3

CH C O O H OH
O
O 2/ 
+
H /H2O
+ CH3 C CH3
Cumene Cumene
(Isopropylbenzene) hydroperoxide
Physical Properties
Alcohols and phenols both are water soluble due to their ability to form H-bond with water. The solubility
decreases with increase in size of hydrophobic group which resist the formation of hydrogen bond with water
molecules. Due to the same reason their boiling points are also greater than corresponding compounds of
similar molecular mass except carboxylic acids. They are polar and protic in nature.
Example 2 : Arrange the following as mentioned

OH O Cl
(a) (i) (ii) (iii) OH (iv)
(increasing order of boiling points)

OH OH
(b) (i) OH (ii) HO OH (iii) HO (iv) HO
(increasing order of solubility in water)

Solution : (a) (i) < (iv) < (ii) < (iii)
(b) (i) < (iv) < (iii) < (ii)
Para isomer is more susceptible to form inter-molecular H– bond with water and therefore more
soluble
Chemical Properties
Chemical properties of alcohols are contributed mainly due to following cleavages:-
Reaction involving RO H bond cleavage
(1) Acidity of alcohols and phenols:

(i) Reaction with metals : Alcohol and phenol reacts with active metals such as sodium, potassium
and aluminium to yield corresponding alkoxide/phenoxide and hydrogen.
1
CH3 – CH2 – OH + Na  CH3CH2 – ONa + H
2 2
CH3 CH3
6CH3 – C – OH + 2Al 2 CH3 – C – O Al + 3H2
CH3 CH3 3
tert-Butyl alcohol Aluminium tert-butoxide
OH ONa
2 + 2Na 2 + H2
Sodium phenoxide
The given reaction shows that alcohols and phenols are bronsted acids i.e., they can donate a proton
to a stronger base (B )
–
B +H–O–R B– H + –R
Base Acid Conjugate Conjugate
acid Base
(ii) Acidity of alcohols : The acidic character of alcohols is due to the polar nature of O – H bond.
An electron releasing group increases electron density on oxygen tending to decrease the polarity
of –OH bond. This decreases the acid strength. Hence acidic strength follows the order :
H H H R
H — C — OH > R — C — OH > R — C — OH > R — C — OH
H H R R
Alcohols are, however weaker acids than water
R—O +H—O—H R — OH + OH
Base Acid Conjugate Conjugate
acid base
This reaction shows that water is a better proton donor than alcohol and an alkoxide ion is a better
proton acceptor than hydroxide ion.
(iii) Acidity of phenols : The hydroxyl group of phenol is directly attached to the sp2 hybridised carbon
of benzene ring which acts as an electron withdrawing group.
O–H O–H O–H O–H O–H
Due to resonance oxygen acquires positive charge thus facilitate the release of H+.
–
OH O
+
+H
Phenoxide ion is also resonance stabilised

O O O O O
Both phenol and phenoxide ion are resonance stabilised but due to charge separation phenol is
less stable than phenoxide ion so it readily releases H+ and forms phenoxide ion.
In substituted phenols, the presence of electron withdrawing groups such as –NO2, –CN, –CHO
enhances the acidic strength of phenol. This effect is more pronounced when such a group is
present at ortho and para positions. It is due to the effective delocalisation of negative charge.
OH OH OH OH
NO2 NO2 NO2 NO2
< < <
NO2 NO2
Electron releasing group such as alkyl groups does not favour the formation of phenoxide ion
resulting in decrease in acid strength.
OH OH OH OH
CH3 CH3 CH3 CH3
> > >
CH3 CH3
Compound Formula pKa
o-Nitrophenol o-O2 N–C6H4–OH 7.2
m-Nitrophenol m-O 2N–C6 H4 –OH 8.3

p -Nitrophenol p-O2 N–C6H4–OH 7.1
Phenol C6H 5–OH 10.0
o -Cresol o-CH3 –C6 H4 –OH 10.2
m-Cresol m-CH3–C6H 4–OH 10.1
p -Cresol p-CH3 –C6 H4 –OH 10.2
Ethanol C2H 5OH 15.9
From the above data, you will note that phenol is million times more acidic than ethanol.
Example 3 : Arrange the following in decreasing order of acidic nature of

(a) (i) F3CCH2OH (ii) (CH3)3CCH2OH (iii) FCH2CH2CH2OH
OH OH
OH OH
NO2
(b) (i) (ii) (iii) (iv)
CH3
OCH3
Solution : (a) (i) > (iii) > (ii)
(b) (ii) > (i) > (iii) > (iv)
—NO2 is stabilizing O– by strong electron withdrawing nature, — CH3 is destabilizing by
electron donating nature (+ I) and — OCH3 is also destabilizing due to electron donting nature
(+ R, – I).
(2) Esterification
Alcohols and phenols both react with acids, acid chlorides and acid anhydrides to form esters. With
carboxylic acids esterification is carried with little amounts of conc. H2SO4;
+
H
R OH + R' COOH R' COOR + H2O
Conc. H2SO4 helps here in two ways that we can understand from the mechanism:
+
O OH OH2
+ (– H2O) +
R C O–H+H R' C OH R' C OH R' C O H
+
O OR OR
+ H R O
O–H
R' C OR +
R – C – OH R' – O – H (–H )
H2SO4 first helps to generate carbocation to facilitate nucleophilic attack and then absorbs water, being
dehydrating agent, to shift the equilibrium towards forward.
This same esterification with acid-chlorides is carried in presence of base pyridine that consumes acid
and shifts the reaction towards forward again.
O O
N
R OH + R' C Cl R' C OR + HCl
The introduction of acetyl group (CH3CO) in alcohols or phenols is known as acetylation. Acetylation of
salicylic acid produces aspirin.
COO H COO H
OH
+
H
+ (CH3CO)2 O + CH 3COO H
Salicylic Acetylsalicylic acid
acid (Aspirin)
Reactions involving R O bond cleavage :
This reaction is given by alcohols only.

(i) Reaction with HX :
Alcohols reacts with HX to form alkyl halides
ZnCl
CH3 OH  HCl 
2
CH3Cl  H2O
CH3CH2OH + HBr  CH3CH2Br + H2O
ZnCl2
CH3 – CH – OH + HCl CH3 – CH – Cl + H2O
CH3 CH3
(ii) Reaction with PCl3 and PCl5 :

3R — OH + PCl3 3R — Cl + H3PO3
ROH + PCl5 R — Cl + POCl3 + HCl
(iii) Reaction with SOCI2:
R Cl + SO2 + HCl (Darzen's process)
R OH + SOCl2
N
Cl R + SO2 + HCl
(SN2)
(iv) Dehydration : Alcohols undergoes dehydration to form alkene on treating with a protic acid
e.g., conc. H2SO4 and H3PO4 or Al2O3. or anhydrous ZnCl2
Ethanol undergoes dehydration by heating it with conc. H2SO4 at 443 K.
H2SO4
C2H5OH 
443 K
 CH2  CH2  H2O
Secondary and tertiary alcohols are dehydrated under milder conditions.
OH
85% H3PO4
CH3 – CH – CH3 440 K
CH3 – CH = CH2 + H2O
CH3
20% H3PO4
(CH3–
) 3 – C – OH 358 K
CH3 – C = CH2 + H2O
Thus the relative ease of dehydration follows the order 1° alcohol < 2° alcohol < 3° alcohol
Mechanism :
Step I : Formation of protonated alcohol
H H H H
+ Fast
H–C–C–O–H+H H–C–C–O–H
H H H H H
(Ethly oxonium ion)
Step II : Formation of carbocation
H H H H
Slow
H–C–C–O–H H – C – C + H2O
H H H H H
Step III : Formation of ethene by elimination of a proton
H H
H H +
H–C–C C=C +H
H H
H H
To drive the equilibrium to the right, ethene is removed as it is formed.

(v) Oxidation: 1° alcohol gives first aldehyde of same carbon, 2° which on further oxidation gives carboxylic acid.
OH
[O] [O]
RCH2 – OH RCHO R–C=O
For this conversion any of the following reagent can be used:
(i) KMnO4/ OH– /  followed by hydrolysis
(ii) KMnO4 / H+
(iii) K2Cr2O7 / H+
(iv) Conc. HNO3
 Here the oxidising agents should be weaker one otherwise aldehyde will further oxidise to the level
of carboxylic acid. The specific oxidising agents is Pyridinium chlorochromate
(PCC). N + HCl + CrO3
PCC
RCH2  OH   RCHO
Secondary alcohols are oxidised to ketones by CrO3.

R [O] R
CH OH C O
R R
 When the vapours of a 1° or 2° alcohol are passed over heated copper at 573 K, dehydrogenation
takes place and an aldehyde or ketone is formed while 3° alcohols do not oxidise, under vigorous
oxidative conditions they undergo elimination.
Cu
R – CH2OH 573 K
RCHO + H2
Dehydrogenation
Cu
R – CH – R 573 K
R – C – R+ H2
OH O
R R
Cu
R – C – OH 573 K
R – C + H2O (Dehydration)
CH3 CH2
 MnO2 selectively oxidises the –OH group of allylic and benzylic 1° and 2° alcohols to aldehydes
and ketones respectively.
EXERCISE
1. Ketones can be converted to tertiary alcohols by
(1) Reduction (2) Oxidation
(3) Reaction with Grignard reagent (4) All of these
+
H2O/H
2. In the sequence of reactions, MgBr + CH2 – CH2 A B . The product B is
O
(1) Benzyl alcohol (2) 2-phenyl ethanol
(3) 1-phenyl ethanol (4) Quinol
3. Iso-butylene when subjected to hydroboration oxidation reaction yields
(1) Sec-butyl alcohol (2) Tert-butyl alcohol
(3) Iso-butyl alcohol (4) n-butyl alcohol
Cl2 /H2O aq. KOH

4. Identify the final product, CH2  CH2   X  Y
(1) 2-chloroethanol (2) 2-chloromethanol
(3) 1-chloroethanol (4) Ethylene glycol
5. 3-methyl-1-butene on oxymercuration-demercuration yields _______ as the major product.
(1) 3-methyl-2-butanol (2) 2-methyl-2-butanol
(3) 3-methyl-1-butanol (4) 2-methyl-1-butanol
6. What is Z in the following sequence of reactions?

PCl alc. KOH (i) conc. H2SO4
Z 
5
 X  Y 
(ii) H O ; boil
Z
2
(1) CH3CH2CH2OH (2) CH3CHOHCH3
(3) (CH3CH2)2CHOH (4) CH3 – CH = CH2
7. Which of the following is the strongest base?
(1) tert-butoxide (2) Ethoxide
(3) iso-propoxide (4) Methoxide
8. An alcohol on vigorous oxidation is found to give ethanoic acid and propanoic acid. The alcohol may be
(1) 1-pentanol (2) 2-pentanol
(3) 1-butanol (4) 2-butanol
9. The order of reactivity of alcohols with sodium metal is
(1) 3° > 2° > 1° (2) 1° > 2° > 3°
(3) 2° > 3° > 1° (4) 3° < 2° > 1°
10. Which one of the following compounds would not be easily oxidised by K2Cr2O7 in dil. H2SO4?
(1) CH3OH (2) (CH3)3COH
(3) CH3CH2OH (4) CH3CHO
11. Which of the following alcohols can be most easily dehydrated?

(1) C2H5OH (2) CH3 – CH – OH
CH3
CH3
(3) CH3 – C – OH (4) CH3CH2CH2OH
CH3
12. When wine is put in air, it becomes sour due to
(1) Bacteria (2) Oxidation of C2H5OH to CH3COOH
(3) Virus (4) Formic acid formation
13. Which of the following enzymes converts starch into maltose?

(1) Zymase (2) Maltase
(3) Diastase (4) Invertase
14. Rectified spirit is a mixture of
(1) 95% C2H5OH and 5% H2O
(2) 94% C2H5OH and 6% H2O
(3) 95.87% C2H5OH and 4.13% H2O
(4) 94.47% C2H5OH and 5.53% H2O
15. Methanol and ethanol can be distinguished by
(1) Lucas test (2) Iodoform test
(3) Victor Meyer’s test (4) All of these
Reactions of Phenols
 Electrophilic Aromatic Substitution: Due to electron donating nature of –OH group, benzene ring of
phenol is activated towards electrophilic aromatic substitution reactions. Some important reactions of this
category are:
(i) Nitration : With dil. HNO3 acid at low temperature (298 K) phenol yields a mixture of –o and p–
nitrophenols.
OH OH
NO2
dil HNO3
298 K +
OH
(major)
NO2
OH
O2N NO2
conc. HNO3 or
(conc. HNO3 + conc. H2SO4)
NO2
(Picric acid)
With concentrated HNO3, phenol is converted to 2, 4, 6-trinitrophenol.
Note :
 The ortho and para isomers can be separated by steam distillation. o-nitrophenol is steam
volatile due to intramolecular H-bonding while p-nitro phenol is less volatile due to
intermolecular H-bonding.
 Yield of formation of picric acid can increase by treating phenol first with conc. H2SO4 followed
by reaction with conc. HNO3.
(ii) Halogenation : When phenol is treated with Br2 in solvents of low polarity such as CHCl3 or CS2
and at low temperature monosubstituted phenols are formed.
OH OH OH
Br
CS2/Br2
273 K +
Br
(major)
Mechanism :
–  – 
+
OH + Br Br Br + Br
Here polarity of phenol is responsible for the generation of Br+ (the electrophile) so reaction takes
place even in the absence of Lewis acid.
OH OH OH
H Br
+
Br Br
+ + H+
If the same reaction proceeds in aqueous (polar) medium then more Br+ generate and phenol
undergoes complete bromination and results into the formation of 2, 4, 6-trinitrophenol
OH OH
Br Br
(H2O + Br2)
Br
2, 4, 6-Tribromophenol
(iii) Kolbe’s Reaction : Phenol when treated with NaOH it gives phenoxide ion which is more reactive
than phenol, hence it undergoes electrophilic substitution reaction with CO2, a weak electrophile.
Orthohydroxy benzoic acid is formed as the main product.
OH OH O OH
NaOH / CO2 C OH
H2O +
(major)
2-hydroxy COO H
benzoic acid
(Salicylic acid)
(iv) Reimer-Tiemann Reaction : On treating phenol with CHCl3 in the presence of NaOH a –CHO
group is introduced at o-position of benzene ring.
O
OH OH OH
C H
CHCl3/KOH(alc.)
H2O +
(major)
CHO
Mechanism:
alc. KOH
CHCl3 CCl2 (elimination) + KCl + H2O
OH OH OH OH OH OH O
H CHCl2
CH C—H
CCl2 CCl2 H2O (–H2O)
OH
benzal chloride Salicylaldehyde
(v) Reaction of phenol with zinc dust (Reduction) :

OH

+ Zn + ZnO
This is also the method of preparation of benzene.

(vi) Oxidation : By application of strong oxidising agents phenol converts into conjugated diketone
known as benzoquinone. In the presence of air phenols are slowly oxidised to dark coloured mixtures
containing quinones.
OH
+
K2Cr2O7/H
O O
benzoquinone
Glycerol:
1, 2, 3–Propanetriol is a colourless, odourless syrupy, sweet liquid. It is highly soluble in water due to
extensive H-bonding. It occurs in nature in oils and fats which are triesters or glycerides of higher fatty acids
like stearic acid (C17H35COOH), palmitic acid (C15H31COOH) etc.
Methods of Preparation:
(1) By hydrolysis - Alkaline hydrolysis is called saponification which converts an oil or fat into free glycerol
and soap.
CH2OCOR CH2OH

CH2OCOR + 3NaOH (aq.)
CHOH +3RCOONa
CH2OCOR CH2OH Soap
(2) Synthesis from propene

CH3 – CH = CH2 
Cl2 /770K
 ClCH2 — CH = CH2 
Aq. NaOH
 HOCH2 — CH = CH2
 CH 2 – CH – CH 2OH glycerol
HOCl NaOH(aq.)
 CH 2 – CH – CH2OH 
OH Cl OH OH
Reactions :
CH2ONO2
HNO3, H2SO4,298 K
CHONO2 Glyceryl trinitrate
CH2ONO2 I I
3HI –I2
CH2 = CH – CH2I CH3 –CH–CH2 CH3 –CH=CH2 + HI CH3 –CH(I)–CH3
–I2 HI
Allyl iodide Isopropyl iodide
CH2OH
dehydration
CHOH CH2 = CH – CHO Acrolein
KHSO4
CH2OH
Oxalic acid
HCOOH + H2O
383 K
Oxalic acid
CH2 = CH – CH2OH
503 K
Allyl alcohol
Oxidation reactions of Glycerol :

COOH COOH
dil. HNO3
CHOH + CHOH
CH2OH COOH
Glyceric acid Tartronic acid
conc. HNO3
Glyceric acid
COOH
Bi(NO3)3
CH2OH CO Mesoxalic acid
CHOH COOH
CH2OH CHO CH2OH
Fenton's reagent (This mixture is also called glycerose)
(FeSO4 + H2O2)
CHOH + CO
CH2OH CH2OH
Glyceraldehyde Dihydroxy-
acetone
A mixture of glycerol trinitrate and glycerol dinitrate absorbed on porous earth is known as dynamite, which is
an explosive.
Glycerol is used in medicines, cosmetic and textile processing.

Test of distinguishing 1°, 2° and 3° alcohols
Lucas Test
Alcohols react with concentrated hydrochloric acid in the presence of anhydrous zinc chloride to form alkyl
chlorides. The alkyl chlorides appear as cloudiness because of its insolubility in Lucas reagent.
ZnCl2
R – OH  HCl 
 conc HCl
 R  Cl  H2O
alkyl halide 
cloudiness
The three types of alcohols undergo this reaction at different rates. The rates of reaction with Lucas reagent
[conc. HCl + ZnCl2 (anhydrous)] follow the given order.
Tertiary alcohol > Secondary alcohol > Primary alcohol
An unknown alcohol (monohydric) is mixed with conc. HCl and anhydrous ZnCl2 at room temperature. The
alkyl chloride formed is insoluble is the medium, thus the solution becomes cloudy before it separates out
as a distinct layer. The following observations are made,
(a) If cloudiness (white turbidity) appears immediately, the alcohol is tertiary.
(b) If cloudiness appears within 5 minutes, the alcohol is secondary.
(c) If the solution remains clear, i.e., no cloudiness is formed the alcohol is primary.
Victor Meyer’s Test
In the test, the following steps are involved,
(i) Alcohol is reacted with conc. Hl or red phosphorous and iodine to form corresponding alkyl iodide.
(ii) Alkyl iodide is then treated with silver nitrite when corresponding nitroalkanes formed.
(iii) Nitro alkane is treated with nitrous acid (NaNO2 + H2SO4) and the solution is made alkaline by addition
of excess of caustic soda.
Primary Secondary Tertiary
RCH2OH R2CHOH R3COH

HI HI HI
RCH2I R2CHI R3Cl

AgNO2 AgNO2 AgNO2
RCH2NO2 R2CHNO2 R3CNO2

HNO2 HNO2 HNO2
RC–NO2 R2C–NO2 No reaction
HaOH
NOH N O
Nitrolic acid Pseudonitrole Colourless
NaOH NaOH
Blood red colour Blue colour
EXERCISE
16. In Reimer Tiemann reaction dichlorocarbene acts as
(1) Nucleophile (2) Electrophile
(3) Free radical (4) All of these
17. Carbolic acid is
(1) Phenol (2) Phenyl benzoate
(3) Phenyl acetate (4) Salol
18. Which of the following is a trihydric phenol?
(1) Resorcinol (2) p-cresol
(3) Phloroglucinol (4) Catechol
19. Which of the following is the strongest acid?
OH
OH
(1) (2)
CN
Cl
OH OH
(3) (4)
NO2
NO2
20. Electrophilic substitution in phenol takes place at
(1) Ortho and para positions (2) Meta-position
(3) Ortho-position (4) Para-position
21. The following reaction is known as
CHCl /NaOH
Phenol 
3
  Salicylaldehyde
H
(1) Gattermann aldehyde synthesis (2) Sandemeyer’s reaction

(3) Kolbe’s reaction (4) Reimer-Tiemann reaction
22. What amount of bromine will be required to convert 2 g of phenol into 2, 4, 6-tribomophenol?
(1) 4.0 (2) 6.0
(3) 10.22 (4) 20.44
23. Identify the product Z in the following sequence of reactions
OH +
NaOH CO2 H3O
X 4-7 atm
Y Z
410 K
(1) Aspirin (2) Salicylaldehyde
(3) Benzoic acid (4) Salicylic acid
24. Phenol can be distinguished from ethyl alcohol by all reagents except
(1) NaOH (2) FeCl3
(3) Br2 /H2O (4) Na
25. The most suitable method of separation of a 1 : 1 mixture of o- and p-nitrophenols is
(1) Sublimation (2) Chromatography
(3) Crystallisation (4) Steam distillation
26. Neutral FeCl3 gives purple colour with
(1) Only phenol (2) p-cresol
(3) 2, 4, 6-tribromophenol (4) All of these
27. Aspirin is obtained by the reaction of salicylic acid with
(1) Acetic anhydride (2) Acetaldehyde
(3) Acetyl chloride (4) Methanol
OH
28. Zinc powder + X . In the above reaction the product X will be
(1) Benzaldehyde (2) Benzene (3) Anisole (4) Phenyl acetate

29. The ionization constant of phenol is higher than that of ethanol because
(1) Phenoxide ion is a stronger base than ethoxide ion
(2) Phenoxide ion is stabilized through delocalisation
(3) Phenoxide ion is less stable than ethoxide ion
(4) Phenoxide ion is bulkier than ethoxide ion
Zn
30. X 
; X can be
OH
OH OH
(1) (2) (3) (4) All of these

OH
OH
SOME COMMERCIALLY IMPORTANT ALCOHOLS
1. Methanol : (Wood spirit):

(ZnO + Cr2O3)
CO + 2H2 200 – 300 atm
CH3OH
573 – 673 K
It is highly poisonous in nature, causes blindness and even death. It is used as a solvent in paints and
varnishes.
2. Ethanol :
It is obtained commercially by fermentation of sugars. The sugar is molasses.
Invertase
C12H22O11   C6H12O6  C6H12O6
glucose fructose
Glucose and fructose undergoes fermentation in the presence of zymase, which is found in yeast.
Zymase
C6H12 O6  C2H5 OH  2CO2
The action of zymase is inhibited once the percentage of alcohol reaches 14% under anaerobic
(absence of O2) conditions. If air gets into fermentation mixture, the O2 oxidises ethanol to ethanoic acid,
which destroys the taste of alcoholic drinks. The commercial alcohol is made unfit for drinking by mixing in
it some CuSO4 (to give it a colour) and pyridine (a foul smelling liquid). It is known as denaturation of alcohol.
ETHERS
Classification: Ethers are classified as simple or symmetrical, if the alkyl or aryl group attached to the oxygen
atom are the same, and mixed or unsymmetrical, if the two groups are different.
O
Symmetrical ether : C2H5OC2H5,
O – C2H5
Unsymmetrical ether : CH3 – O – C2H5,
Naming of Ethers : Common names of ethers are derived from the names of alkyl/aryl groups written as
separate words in alphabetical order and adding the word ether at the end.
Example : CH3 – O – C2H5 ethylmethyl ether
C2H5 – O – C2H5 diethyl ether
According to IUPAC system of nomenclature, ethers are regarded as hydrocarbon derivatives in which a hydrogen
atom is replaced by an –OR or –OAr groups. The larger (R) group is chosen as the parent hydrocarbon.
Example : CH3 – O – CH3 – Methoxymethane
CH3CH2 – O – CH2CH3 – Ethoxyethane
O – CH3
– Methoxybenzene
Structure of Functional Groups : In ethers, the two bond pairs and two lone pairs of electrons on oxygen
are arranged approximately in a tetrahedral arrangement. The bond angle is slightly greater than the tetrahedral
angle due to (bp-bp-repulsion) the repulsive interaction between the two bulky (–R) groups. The (C – O) bond
length is almost the same as in alcohols.
141 pm
..
..
O CH3
CH3
111.7º Methoxymethane
Preparation of Ethers
1. By inter-molecular dehydration of alcohols : Alcohols undergo dehydration in presence of protic acid.
H2SO4
CH2 CH2
443 K
CH3CH2OH
H2SO4
C2H5OC2H5
413 K
The formation of ether is a nucleophilic bimolecular reaction, as indicated below
H
+
Step I : CH3CH2 – O – H + H CH3CH2 – O – H
H
Step II : CH3CH2 – O + CH3CH2 – O CH3CH2 – O – CH2CH3 + H2O
H
H H
+
Step III : CH3CH2 – O – CH2CH3 CH3CH2 – O – CH2CH3 + H
H
This method is suitable for the preparation of ethers having 1° alkyl groups only. The dehydration of
2° and 3° alcohol give alkenes as major product.
2. Williamson’s synthesis : It is an important method to prepare all types of ether. Alkyl halide is
allowed to react with sodium alkoxide.
RO– Na+ + X — R' R O R'
This is a nucleophilic substitution reaction which undergoes via SN2 as
– +
RO Na –
CH2 X RO ----CH2-----X– ROCH2R
R
Better results are obtained if the alkyl halide is 1°. In case of 2° alkyl halide, elimination competes
over substitution. If a 3° alkyl halide is used, an alkene is the major product and no ether is formed.
CH3
CH3 – C – Br + NaO – CH3 CH3 – C = CH2 + NaBr + CH3OH
CH3 CH3
Phenols are also converted to ethers by this method. Phenol is used as the phenoxide moiety.
OH ONa
+ NaOH
ONa O–R
+R–X
Example 4 : a. When 3° alkyl halide is used in Williamson’s synthesis what will be the major product
and why ?
b. When 3° alkoxide is used in Williamson’s synthesis what will be the major product and why ?
Solution : a. Tendency of elimination of alkyl halides increases in the order of 3° > 2° > 1°, so major
product will be alkene.
b. When 3° alkoxide is used with 1° alkyl halide ether is obtained as major product.
Physical Properties
Due to large size of alkyl groups (than H) R – O – R bond angle in ethers is large ( > 110°) therefore net
dipole-moment becomes less and therefore ethers show:
(i) Low boiling points
(ii) Low solubility in water
Solubility in water further decreases with increasing molar mass of ethers as etheral oxygen becomes more
hindered and become less available to inter-molecular H-bonding with water.
Chemical Properties
(I) Cleavage of C–O Bond in Ethers: Ethers due to low polarity are least reactive among other functional
groups. With strong acids they form alkyl halide and alcohols by “C — O” bond cleavage:
HX
RCH2 — O — CH2R RCH2OH + RCH2 — X
Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable aryl oxygen bond.
O–R OH
+H–X +R–X
Ethers with two different alkyl groups are also cleaved in similar manner.
CH3 – O – CH2CH3 + HX  CH3X + CH3CH2OH
The order of reactivity of hydrogen halides is as follows :
HI > HBr > HCl
Mechanism : The reaction of an ether with concentrated HI starts with protonation of ether.
H
–
Step I : CH3 – O – CH2 – CH3 + HI CH3 – O – CH2CH3 + I
Step II : Iodide is a good nucleophile. It attacks the least substituted carbon of the oxonium ion
formed.
H
–
SN2
I + CH3 – O – CH 2CH 3 CH3I + CH3CH2OH
When HI is in excess and the reaction is carried out at high temperature, ethanol reacts with
another molecule of HI and is converted to ethyl iodide.
H
–
Step III : CH3 – CH2 – O – H + HI CH3 – CH2 – O – H + I
CH3
–
I + CH2 – OH2 CH3CH2I + H2O
However, when one of the alkyl group is a tertiary group, the halide formed is a tertiary halide.
CH3 CH3
SN1
CH3 – C – O – CH3 + HI CH3OH + CH3 – C – I
CH3 CH3
In case of anisole,
H OH
OCH3 + HI O – CH3
+ CH3I
The bond between O – CH3 is weaker than the bond between O – C6H5, hence I– attack
breaks O – CH3 bond to form CH3I and phenol. Phenols do not react further to give halides
because the sp2 hybridised carbon of phenol cannot undergo nucleophilic substitution reaction
to the halide.
Example 5 : a. What is the reactivity order of given halogen acids towards ethers?
HCl, HBr, HI
b. What will be final products ?
CH3
 
(i) O CH3 + HI (ii) CH3 C O CH3 + HI
CH3

(iii) CH3CH2 — O — CH3 + HI 
Solution : a. HI > HBr > HCl
b. (i) OH + CH3I (SN2)
(ii) CH3OH + (CH3)3 C — I (SN1)
(iii) CH3CH2OH + CH3 I (SN2)
(II) Electrophilic substitution (Reactions of Aryl Ethers): Aryl ethers show the reactions like phenols as
– OR is also an activating group. The electrophilic substitution shown by aryl ethers are:
(i) Halogenation
(ii) Friedel-Crafts Reaction
(iii) Nitration
OCH3 OCH3 OCH3

O
Br
(i) Br2 / CH3 C OH
+
Br
OCH3 OCH3 OCH3

CH3
(ii) CH3Cl/AICl3 (anhyd)
+
CH3
This is known as Friedel-Craft alkylation
OCH3 OCH3 OCH3
O
COCH3
CH3C Cl/AICl3 (anhydrous)
+
COCH3
This is known as Friedel-Craft acylation
OCH3 OCH3 OCH3
NO2
(iii) (conc. H2SO4 + conc. HNO3)
+
NO2
Mechanism for all these reactions is same as in case of phenols as all of them are electrophilic aromatic
substitution. In all these four reactions para isomer is major product.
EXERCISE
31. How many metamers of formula C4H10O are possible?
(1) 2 (2) 3
(3) 4 (4) 1
32. Which of the following has maximum bond angle around oxygen?
(1) CH3 – O – CH3 (2) C2H5 – O – C6H5
O
(3) (4) Same in all
33. – OCH3 group is

(1) Stronger +R group than – OH (2) Weaker +R group than –OH
(3) Stronger +I group than – OH (4) Inert group

34. CH3CH2  Cl  Ag2O   Product . Product formed in the reaction is
(1) CH3CH2 – O – CH2CH3 (2) CH3CH2Cl + AgCl

(3) CH3CH2 – OH + AgCl (4) (CH3CH2 – O)2 Ag
ONa Cl heat
35. + Product . Product of the reaction is
O OH
(1) (2) +
O Cl
(3) (4) No reaction
36. The ether that undergoes electrophilic substitution reaction is
(1) CH3OC2H5 (2) C6H5OCH3
(3) CH3OCH3 (4) C2H5OC2H5
37. When ether is exposed in air for sometime, an explosive substance produced is
(1) Peroxide (2) TNT
(3) Oxide (4) Superoxide
38. An ether is more volatile than an alcohol having the same molecular formula. This is due to
(1) Inter-molecular hydrogen bonding in alcohols
(2) Dipolar character of ethers
(3) Alcohols having resonance structure
(4) Inter-molecular hydrogen bonding in ether
39. Anisole with HNO3 and conc. H2SO4 gives

(1) Phenol (2) Nitrobenzene
(3) o- and p-nitroanisole (4) o-nitroanisole
40. Williamson’s synthesis involves
(1) SN1 mechanism (2) SN2 mechanism

(3) Nucleophilic addition (4) Electrophilic addition
Note :
1. Alcohols are stronger acids than acetylene, because alcohols displace the weaker acetylene. The order
of acidity is H2O > ROH > HC  CH. But CH3OH is stronger acid than H2O because Ka value is high for
CH3OH.
2. Alcohols react with carboxylic acids in presence of conc. H2SO4 to form an ester. The bulkier the acid
or alcohol, the slower is the rate of esterification. The ease of ester formation follows the order : Primary
alcohol > Secondary alcohol > Tertiary alcohol. Similarly, HCOOH > CH3COOH > CH3CH2COOH >
(CH3)2 CHCOOH > (CH3)3 CCOOH.
3. Pyroligenous acid is a mixture of CH3OH, CH3COCH3 and CH3COOH, along with water.
4. Gasohol, a mixture of gasoline and ethyl alcohol, is used as a motor fuel.
5. Tincture of iodine is a mixture of I2 + KI + H2O + C2H5OH.
6. The dehydrating agent to be used to remove water from alcohol is quick lime (CaO) or magnesium
ethoxide (C2H5O)2Mg.
7. When phenols are heated with phthalic anhydride in presence of Conc. H2SO4, anhy. ZnCl2 or Al2O3,
phthaleins with characteristic colours in alkaline medium are obtained. For example, phenol gives
phenolphthalein (a dye and indicator) and resorcinol gives fluorescein.
8. Phenol is used as antiseptic. It is also used as starting material in the manufacture of nylon, plastics,
aspirin, picric acid (an explosive) and salicylic acid etc.
9. Pyrogallol is used as a photographic developer and for the absorption of oxygen.
10. Fries rearrangement :
OCOCH3 OH OH
COCH3
Anhyd. AlCl3, CS2
+

Phenyl acetate o-Hydroxyacetophenone COCH3

p-Hydroxyacetophenone
OH
OCOC6H5 OH
COC6H5
Anhyd. AlCl3, CS2
+

Phenyl benzoate o-Hydroxybenzophenone COC6H5

p-Hydroxybenzophenone
Generally low temperatures (330 K or less) favour the formation of p-isomer, whereas high temperatures
(430 K or above) favour the formation of o-isomer.
  
t
en
nm nment
sig ssig
As A Assignment
Assignment
4. Consider the following reaction. [NCERT Pg. 331]
SECTION - A
O
NCERT Based MCQs || (i) CH3MgBr(excess)
Ph  C  OCH3 (ii) H O
P
1. Catechol is [NCERT Pg. 327] 3
Product P is
OH OH O
OH ||
(1) (2) (1) Ph  C  CH3
OH
OH
OH OH |
(2) Ph  C  CH3
|
(3) (4) CH3
OH
OH CH 3 (3) (CH3)3C – OH
(4) (Ph)3C – OH
2. Product (A) obtained in the given reaction is
[NCERT Pg. 332] 5. Correct order of acidic strength is
+ –
[NCERT Pg. 337]
N2Cl
OH OH OH OH
H2O/ 
Product (A) + N2 + HCl NO 2 NO2
(1) < < <
Cl OH
CH3 NO2 NO 2
(1) (2)
OH OH OH OH
Cl Cl O 2N NO2
OH (2) < < <
(3) (4)
CH3 NO2 NO 2
OH
3. On treating phenol with chloroform in the presence OH OH OH OH
of aq. NaOH, the major product formed after acidic NO 2 NO 2
work up is [NCERT Pg. 343] (3) < < <
OH OH
Cl CHO CH3 NO 2 NO2
(1) (2)
OH OH OH OH
OH OH O2N NO 2
(4) < < <
(3) (4)
CH3 NO 2 NO 2
CHO OH
6. The compounds added in commercial alcohol to H2SO4

made unfit for drinking is/are [NCERT Pg. 344] 12. CH3CH2OH 
413 K
A
(1) Copper sulphate (2) Pyridine

Product A is [NCERT Pg. 338]
(3) H2SO4 (4) Both (1) and (2)
(1) CH2 = CH2 (2) CH3CH2OCH3
7. Oxidation of phenol with chromic acid gives
[NCERT Pg. 343] (3) CH3CH2OCH2CH3 (4) All of these
(1) Benzaldehyde (2) Benzoic acid 13. Fermentation of glucose and fructose in presence
of zymase gives [NCERT Pg. 344]
(3) p-Benzoquinone (4) Acetophenone
8. On treating phenol with chloroform in presence of (1) CH3OH (2) CH3CH2OH
sodium hydroxide the intermediate formed is
[NCERT Pg. 343] (3) CH3OCH3 (4) CH3CH2OCH3
OH ONa 14. Which of following ether cannot be produced by

CHCl 2 CHCl 2 Willamson synthesis? [NCERT Pg. 345]
(1) (2)
(1) CH3OCH3
ONa OH
CHO CHO (2) OCH 3
(3) (4)
9. Cumene is [NCERT Pg. 332] (3) O
CH2CH3 CH 3 – CH – CH 3
(1) (2) (4) O
15. Most acidic among the following is

[NCERT Pg. 337]
C (CH3)3 CH 2CH 2CH3
(1) Phenol (2) o-Cresol
(3) (4)
(3) m-Cresol (4) p-Cresol
10. IUPAC name of the compound [NCERT Pg. 327]
CH 3O – CH – CH 3 is SECTION - B
CH 3
Objective Type Questions
(1) 1-Methylmethoxyethane
1. Which of the following is among phenols?
(2) 2-Methoxypropane
(1) o-xylene (2) Resorcinol
(3) 1-Methoxypropane
(3) Anthranilic acid (4) p-benzoquinone
(4) Methyl isopropyl ether
2. Which of the following is least acidic?
11. The ortho and para isomers of nitrophenol can be
OH OH
separated by steam distillation because
[NCERT Pg. 341]
(1) o-Nitrophenol is more water soluble than (1) (2)
p-Nitrophenol F Cl
(2) o-Nitrophenol is less volatile than OH OH
p-Nitrophenol
(3) o-Nitrophenol is steam volatile (3) (4)
(4) o-Nitrophenol has intermolecular H-bonding Br l
3. Which of the following has the greater bond angle 1. B H /THF
around oxygen than normal tetrahedral angle? 8. CH3  CH  CH2 
2 6

A
2. H2O2 /OH
(1) H O (2) CH O
H 3 H NaCN H O
  B 
3
C
O (major )
H O
(3) (4) CH CH3
3 What is C ?
4. Which alcohol is most reactive towards Lucas

reagent? (1) CH3 – CH – COOH
CH3
CH3
|
(1) CH3CH2–OH (2) CH3–CH–CH2OH (2) CH3 – CH2 – CH2 – COOH
(3) (CH3)3C–OH (4) CH3–CH–CH2CH3 (3) CH3 – CH – COOH

|
OH COOH
5. Which of the following reagents can't be used for COOH COOH

the reduction of CH3COOH to CH3CH2OH? (4) CH2 – CH2
(1) LiAlH4 / H2O (2) B2H6 / H+ CH2–CH=CH2
(3) H2 / Pd (4) NaBH4 9.
+
H /H2O .
P (Major)
6. When ethylene oxide is reacted with CH3MgBr
followed by hydrolysis then the product formed is The product 'P' is
(1) Ethanol (2) Propanol-1

CH2–CH–CH3 CH2–CH2–CH2–OH
|
(3) Propanol-2 (4) Ethene OH
(1) (2)
7. What is the major product of the following
reaction?
1. H2 O + Hg(OAc)2 OH
CH3 – CH – CH = CH2 –
2. NaBH4 / OH |
CH3 CH–CH2–CH3
(3) (4) All of these
OH
(1) CH3 – C – CH2 – CH3
CH3
H2SO4 NaOH
10. + SO3 A B
OH 
(2) CH3 – CH – CH – CH3 What is B?

CH3 +
OH O– Na
(1) (2)
(3) CH3 – CH – CH2 – CH2 – OH
CH3 –+
OH SO3Na
(4) CH2 – CH – CH2 – CH3 (3) (4)
CH3
15. Which of the following will react with NaHCO3 to

H2SO 4 Sn/HCl
11. + HNO 3 (conc.) A B give salt, water and CO2?
NaNO2+HCl H2O OH
0–5º C C D
(1) (2) CH3 – COOH
What is D?
NH2 OH
OH
(1) (2)
NO2 NO2
COOH
Cl (3) (4) Both (2) & (3)
NO2
(3) (4)
O
16. 18
H
+
12. Which of the following has the highest solubility in R – C – OH + HO – CH3
water? O
18
(1) Phenol (2) o-nitrophenol R – C – O – CH3 + H2O
(3) p-nitrophenol (4) m-nitrophenol 18
In above reaction CH3 O H act as
13. Which of the following is least acidic?
(1) Nucleophile (2) Base
OH
(3) Electrophile (4) Acid
(1) CH3 – COOH (2)
OH O O
COOH
CH3 17. + CH3 – C – O – C – CH3
OH OH
O
(3) (4) H
+
A + CH3 – C – OH
NH2 NO2 What is A?
14. Which of the following is the correct order of acidic
strength? (1) Aspirin (2) D.D.T
OH OH OH OH (3) Oil of wintergreen (4) Salol

NO2 18. Which of the following will not react with Lucas
> > > reagent at room temperature but react at elevated
(1) NO2
temperature?
NO2
(1) CH3 – CH2 – OH
OH OH OH OH
NO2 OH
(2) > > >
NO2 (2) CH – CH – CH
3 3
NO2
OH OH OH OH OH
NO2
> > > (3) CH3 – C – CH3
(3)
NO2
CH3
NO2
OH OH OH OH
OH
NO2
(4) > > > (4) CH3 – CH – CH – CH3
NO2
NO2 CH3
19. In Victor-Meyer test, the blue colouration is shown
CH3
by Cu
25. CH3 – C – OH A + HBr
(1) 1º-alcohol (2) 2º-alcohol 300ºC
CH3
(3) Ethylene glycol (4) 3º-alcohol Mg/dry ether H2O
B C D
20. HBr reacts fastest with What is D?
(1) 2-methyl propan-2-ol
CH2 CH3
(2) Propan-2-ol (1) CH3 – C (2) CH3 – C – Br
(3) Propan-1-ol CH3 CH3
(4) 2-methylpropan-1-ol CH3 CH3
21. When excess of HI is reacted with glycerol then (3) CH3 – C – MgBr (4) CH3 – CH – CH3
the major product formed is
CH3
(1) Allyl iodide (2) Isopropyl iodide
26. Which of the following is the most suitable
(3) Propene (4) Propyl iodide
oxidising agent for the following reaction?
OH
O
H2SO4
22. CH3 – CH – CH2 – CH – CH3 A
453 K CH3 – CH2 – OH CH3 – C – H
(major)
CH3
A is (1) PCC + CH2Cl2 (2) KMnO4/H+
(1) CH 3 – C = CH – CH 2 – CH 3 (3) K2Cr2O7 / H+ (4) All of these
CH3 OH
(2) CH3 – CH – CH = CH – CH3 27. + HNO3 (conc.) A

(major)
CH3
What is A ?
(3) CH 3 – CH – CH2 – CH = CH 2
OH
CH3 NO2
(1)
(4) CH2 = C – CH2 – CH2 – CH3
OH
CH3
(2)
23. Which is of the following is the best suitable NO2
oxidising agent for the following reaction?
OH
OH
CH3 – CH – CH = CH2 (3)
O NO2
CH3 – C – CH = CH2 ? OH
(1) PCC + CH2Cl2 (2) O3 NO2 NO2
(3) KMnO4 / H+ (4) K2Cr2O7 / H+ (4)

24. In presence of bismuth nitrate, glycerol is oxidised NO2
to give 28. Which compound reacts with NaHCO3?
(1) Glyceraldehyde (2) Dihydroxy acetone (1) Phenol (2) o-cresol
(3) Tartronic acid (4) Mesoxalic acid (3) p-cresol (4) 2, 4, 6-trinitrophenol
33. Which of the following group is the strongest ring

OH activator towards electrophilic aromatic
CS2 substitution?
29. + Br2 A
273 K
(major) (1) –OH
A is (2) –NH2
OH OH (3) –OCH3
Br
(1) (2) (4) –Cl
Br
H SO
34. CH3  CH2  OH 
2 4
 A . A is
413K
OH OH
Br Br (1) CH2 = CH2
(3) (4) (2) CH3 – CH2 – O – CH2 – CH3
Br Br
(3) CH3 – CH2 – OSO3H
30. On exposure to air, phenol gives pink colour. It is (4) All of these
due to the formation of
35. CH3 – O – CH – CH3 + HI A +B
(1) Benzoic acid (2) Benzylalconol (alcohol)
CH3
(3) Benzoquinone (4) Benzaldehyde
Which of the following is major product A?
OH
+
(1) CH3 – OH
31. NaOH A + CO2 B
H
C
(2) HO – CH – CH 3
C is CH3
OH
(3) CH3 – CH2 – OH
COOH
(1)
(4) CH3–CH2–CH2–OH
OH Cl
OH – + 1. CH3 MgCl
COONa 36. CH3 – CH – CH2 + Na A B
2. H2 O
(2)
B is
O
– +
O Na (1) CH3 – CH – CH2
+
C–ONa
(3) OH
O
(2) CH3 – CH – CH2 – CH3
O
C–OH (3) CH3 – CH – CH2 – OH
(4)
CH3
32. Which of the following reagent attack on the
benzene ring in Reimer-Teimann reaction?
OH
(1) :CH2 (2) CCl
2 (4) CH 3 – CH – CH 2
(3) :CCl2 
(4) : CCl OH
2
CH3 40. When glycerol is heated with KHSO4, it gives
CH – CH3 (1) CH2=CH–CH3
+
H2O / H
37. + O2 A (2) CH2=CH–CH2OH
(3) CH2=CH–CHO
OH
O
(4) CH2=C=CH2
+ CH3 – C – CH3
41. Which of the following produce violet colour with
A is neutral FeCl3 solution?
(1) Phenol (2) Ethanol
CH3 (3) Ethanal (4) Alkyl halides
(1) H – O – O – C – CH3
42. The O–H group in phenol in an electrophilic
aromatic substitution is
(1) o-directing (2) p-directing
(3) m-directing (4) o & p-directing
OH 43. Molecular formula of amyl alcohol is
O = C – CH – CH3
(1) C7H14O (2) C6H13O
(2)
(3) C5H12O (4) C5H10O
44. Glycerol heated with oxalic acid at 110ºC to form
O (1) Formic acid (2) Oxalic acid
O – C – CH2 – CH3
(3) Allyl alcohol (4) Glycerol trioxalate
(3)
45. Decreasing order of reactivity of alcohols towards
sodium metal is
O
O – CH2 – C – CH3 (1) Primary > Secondary > Tertiary
(4) (2) Tertiary > Secondary > Primary
(3) Secondary > Primary > Tertiary
38. When ethyl alcohol is treated with H2SO4 at 0ºC (4) They are equally reactive
product will be
46. Identify [X] in the following reaction
(1) Ethyl oxonium hydrogen sulphate OH
(2) Diethyl sulphate HCN + HCl
[X]
ZnCl2, H2O
(3) Ethyl hydrogen sulphate OH OH
(4) Ethane OH OH
CHO CHO
39. From Williamson’s synthesis preparation of which (1) (2)
of following is possible OH OH OH
OH
(1) Only symmetrical ethers
OH OH
(2) Only unsymmetrical ethers
OH
(3) Both (1) & (2) (3) (4)
(4) None of these CHO

47. Ethylene glycol, on oxidation with periodic acid 2. The major products C and D formed in the following
gives reaction respectively are
(1) Oxalic acid (2) CO2 + H2O H3C – CH2 – CH2 – O – C  CH3 3 
excessHI

C  D
(3) Formaldehyde (4) Glycolic acid [NEET-2019 (Odisha)]
48. Carbolic acid is (1) H3C – CH2 – CH2 – OH and HO – C(CH3)3
(1) Phenol (2) Phenyl benzoate (2) H3C – CH2 – CH2 – I and I – C(CH3)3
(3) Phenyl acetate (4) Salol (3) H3C – CH2 – CH2 – OH and I – C(CH3)3
49. Arrange the following alcohols according to (4) H3C – CH2 – CH2 – I and HO – C(CH3)3
decreasing order of reactivity in dehydration 3. The structure of intermediate A in the following
reaction reaction, is [NEET-2019]
(I) CH3
CH 3–CH – CH 2 – NO 2 CH OH
CH3 O
OH O2 H
+
A + H 3C CH3
H2O
(II) CH3–CH– CH2–CHO
OH CH 3 CH 3
CH
O – CH H 3C – C – O – O – H
(III) CH 3 –CH – CH 2 –CN 3
OH (1) (2)
O CH3 CH 2 – O – O – H
(IV) CH3–CH–CH2 –C–CH3 O – O – CH HC
CH 3
OH CH3
(3) (4)
(1) I > III > II > IV (2) I > II > III > IV
4. The compound that is most difficult to protonate is:
(3) III > I > II > IV (4) IV > III > II > I
[NEET-2019]
O
SECTION - C (1) H H
Previous Years Questions O
1. The reaction that does not give benzoic acid as (2) H 3C H
the major product is [NEET-2019 (Odisha)]
O
CH2OH +
(3) H 3C CH3
KMnO4/H
(1)
O
(4) Ph H
CH2OH
K2Cr2O7 5. The compound A on treatment with Na gives B,
(2) and with PCl5 gives C. B and C react together to
give diethyl ether. A, B and C are in the order
COCH3 [NEET-2018]
(i) NaOCl
(3) +
(ii) H3O (1) C2H5OH, C2H6, C2H5Cl
(2) C2H5OH, C2H5Cl, C2H5ONa
CH2OH
PCC
(3) C2H5OH, C2H5ONa, C2H5Cl
(4)  Pyridinium 
 chlorochromate  (4) C2H5Cl, C2H6, C2H5OH
 
6. In the reaction [NEET-2018] 9. The heating of phenyl-methyl ethers with HI
– + produces. [NEET-2017]
OH O Na
(1) Ethyl chlorides
CHO
+ CHCl3 + NaOH (2) Iodobenzene
The electrophile involved is (3) Phenol
 

(4) Benzene
(1) Dichloromethyl cation CHCl
2 10. The reaction
(2) Formyl cation CHO  

 OH
NaH
O Na
Me – I
(3) Dichlorocarbene (:CCl2)
s 
Me
(4) Dichloromethyl anion CHCl
2 O
7. Identify the major products P, Q and R in the
following sequence of reactions: [NEET-2018] can be classified as [NEET-2016]
Anhydrous (1) Williamson alcohol synthesis reaction

AlCl3
+ CH3CH2CH2Cl (2) Williamson ether synthesis reaction
(i) O2 (3) Alcohol formation reaction
P (ii) H3O+/
Q+R
(4) Dehydration reaction
P Q R 11. Which of the following reagents would distinguish
CH2CH2CH3 CHO cis-cyclopenta-1, 2-diol from the trans-isomer?
[NEET-2016]
(1) , , CH3CH2 – OH
(1) Aluminium isopropoxide
CH2CH2CH3 CHO COOH (2) Acetone
(3) Ozone
(2) , ,
(4) MnO2
OH 12. Reaction of phenol with chloroform in presence of
CH(CH 3) 2 dilute sodium hydroxide finally introduces which one
, , CH3 – CO – CH3 of the following functional group? [Re-AIPMT-2015]
(3)
(1) –CHCl2
CH(CH 3)2 OH
(2) –CHO
(4) , , CH3CH(OH)CH3
(3) –CH2Cl
8. Which one is the most acidic compound? (4) –COOH
[NEET-2017] 13. Which of the following is not the product of
OH OH
dehydration of OH ? [Re-AIPMT-2015]
(1) (2)
CH3
(1) (2)
OH OH
O2N NO2
(3) (4)
(3) (4)
NO2 NO2
14. Which of the following reaction(s) can be used for (1) CH3–(CH2)3–O–CH2CH3
the preparation of alkyl halides?
(2) (CH3)2CH2–O–CH2CH3
anh. ZnCl
(I) CH3 CH2OH  HCl 
2

(3) CH3(CH2)4–O–CH3
(II) CH3CH2OH + HCl 
(4) CH3CH2–CH(CH3)–O–CH2CH3
(III) (CH3)3COH + HCl 
18. Among the following ethers, which one will produce
anh. ZnCl2
(IV) (CH3 )2 CHOH  HCl   methyl alcohol on treatment with hot concentrated
H ? [NEET-2013]
[Re-AIPMT-2015]
(1) CH3–CH2–CH–O–CH3
(1) (IV) only
CH3
(2) (III) and (IV) only
(3) (I), (III) and (IV) only CH3

(2) CH 3–C–O–CH 3
(4) (I) and (II) only
CH3
15. The reaction
(3) CH3–CH–CH2–O–CH3
CH3 CH3
CH3—C—ONa + CH3CH2Cl
—NaCl (4) CH3–CH2–CH2–CH2–O–CH3
CH3
19. In the following reaction:
CH3
CH3
H2O/H
H3C–C–CH = CH2
CH3—C—O—CH2—CH3
CH3 CH3
A + B
Major Product Minor Product
is called [AIPMT-2015]
The major product is [AIPMT (Prelims)-2012]
(1) Gatterman - Koch reaction
(2) Williamson synthesis CH3

(1) H3C–C – CH–CH3
(3) Williamson continuous etherification process
CH3 OH
(4) Etard reaction
CH3
16. Among the following sets of reactants which one
produces anisole ? [AIPMT-2014] (2) H3C–C – CH2–CH2
(1) CH3CHO; RMgX CH3 OH
(2) C6H5OH; NaOH; CH3I CH3

(3) C6H5OH; netural FeCl3 (3) H3C–C – CH–CH3
(4) C6H5–CH3; CH3COCl; AlCl3 OH CH3
17. Identity Z in the sequence of reactions CH3

(4) CH2–C–CH2–CH3
CH3CH2CH = CH2 
HBr /H2O 2
 Y 
C2H5 ONa
Z
OH CH3
[AIPMT-2014]
20. In the following reactions, 22. Which one is most reactive towards electrophilic
reagent? [AIPMT (Prelims)-2010]
CH3
|
H /Heat CH3
(a) CH3 – CH – CH– CH3   A  B
|  Major
product   Minor
product  (1)
OH
OH
HBr, dark
(b) A  C  D
Product  Product 
Major
in absence of peroxide Minor CH3
CH2OH
The major products (A) and (C) are respectively (2)
[AIPMT (Prelims)-2011]
CH3
CH3
| NHCOCH3
(3)
(1) CH2  C  CH2 – CH3 and
CH3 CH3
|
CH3  C  CH2 – CH3 OCH3
(4)
|
Br
23. Among the following four compounds
CH3 a. Phenol
|
(2) CH2  C  CH2 – CH3 and b. Methyl phenol
CH3 c. m-Nitrophenol
| d. P-nitrophenol
CH2  CH  CH2 – CH3
| The acidity order is [AIPMT (Mains)-2010]
Br (1) d > c > a > b
CH3 (2) c > d > a > b
|
(3) CH3  C  CH – CH3 and (3) a > d > c > b
(4) b > a > c > d
CH3
| 24. When glycerol is treated with excess of HI, it
CH3  C  CH2 – CH3 produces [AIPMT (Mains)-2010]
|
Br (1) 2-iodopropane (2) Allyl iodide
CH3 (3) Propene (4) Glycerol triiodide

| 25. Which one of the following compounds will be most
(4) CH3  C  CH – CH3 and readily dehydrated ? [AIPMT (Mains)-2010]
CH3 O
| (1)
CH3  CH  CH – CH3 CH3
| OH
Br O
21. Which one of the following compounds has the (2)
most acidic nature? [AIPMT (Prelims)-2010] H 3C
OH
CH2OH OH O OH
(1) (2) (3)
CH3
OH
OH
OH CH (4)
(3) (4) CH3 O
26. Which of the following conformers for ethylene 32. Which one of the following compounds is most acidic?
glycol is most stable? [AIPMT (Mains)-2010]
OH OH
H H OH OH
(1) (2) (1) Cl–CH2–CH2–OH (2)
H H H NO2
OH H HH
OH OH OH OH
H OH (3) (4)
H
CH3
(3) (4)
HO H
H HH H H
Questions asked Prior to Medical Ent. Exams. 2005
27. Consider the following reaction, 33. When 3, 3-dimethyl 2-butanol is heated with H2SO4,
PBr alc. KOH the major product obtained is
Ethanol 
3
 X  Y
(i) H SO room temperature

2 4
Z ; (1) 2, 3-dimethyl 2-butene
(ii) H2O, heat
(2) cis and trans isomers of 2, 3-dimethyl 2-butene
(3) 2, 3-dimethyl 1-butene
(1) CH3CH2–O–CH2–CH3 (2) CH3–CH2–O–SO3H
(4) 3, 3-dimethyl 1-butene
(3) CH3CH2OH (4) CH2 = CH2
28. Consider the following reaction 34. Decreasing order of reactivity of hydrogen halide acids
in the conversion of ROH  RX is
CH3Cl Alkaline KMnO4
Phenol   X   Y  Z
Zn dust Anhydrous AlCl3
(1) HCl > HBr > HI > HF
The product Z is [AIPMT (Prelims)-2009]
(2) HI > HBr > HCl > HF
(1) Benzaldehyde (2) Benzoic acid
(3) HF > HCl > HBr > HI
(3) Benzene (4) Toluene
(4) HF > HBr > HI > HCl
29. H2COH.CH2OH on heating with periodic acid gives
35. More acidic than ethanol is
(1) CH3CH2CH2CH2CH2CH2CH2CH3
(1) 2HCOOH (2) CHO
CHO (2) CH3CO2CH2CH3
H (3) CH3COCH2COCH3
(3) 2 C=O (4) 2 CO2
H (4) CH3COCH3
30. The major organic product in the reaction,
36. Which reagent converts propene to 1-propanol?
CH3 – O – CH(CH3)2 + H  Product is
(1) H2O, H2SO4
(1) CH3OH + (CH3)2CHI (2) ICH2OCH(CH3)2 (2) B2H6, H2O2, OH–
(3) Hg(OAc)2, NaBH4/H2O
(3) CH3O C(CH3)2 (4) CH3 + (CH3)2CHOH
(4) Aq. KOH
I
31. Ethylene oxide when treated with Grignard reagent 37. n-propyl alcohol and isopropyl alcohol can be
yields [AIPMT (Prelims)-2006] chemically distinguished by which reagent?
(1) Secondary alcohol (1) PCl5
(2) Tertiary alcohol (2) Reduction

(3) Cyclopropyl alcohol (3) Oxidation with potassium dichromate
(4) Primary alcohol (4) Ozonolysis
38. Which one of the following will not form a yellow
SECTION - D
precipitate on heating with an alkaline solution of
iodine? NEET Booster Questions
(1) CH3CH(OH)CH3 (2) CH3CH2CH(OH)CH3 1. In the given reaction
(3) CH3OH (4) CH3CH2OH Cl
39. The general molecular formula, which represents the Cl
4 SN1
homologous series of alkanols is 3 + CH3OH
O 2 Cl
(1) CnH2n + 2O (2) CnH2nO2
–Cl will be replaced by –OCH3 at carbon
(3) CnH2nO (4) CnH2n + 1O
(1) 2 (2) 3
40. On heating glycerol with conc. H2SO4, a compound (3) 4 (4) Any of these
is obtained which has bad odour. The compound is 2. In the given reaction
(1) Acrolein (2) Formic acid (i) CH3MgBr
CH3 CH CH2 (P)
(3) Allyl alcohol (4) Glycerol sulphate (ii) HOH/H
O
41. The correct acidic order of the following is (P) is
OH OH OH (1) CH 3 – CH – CH 2 OH
I. II. III. CH3

(2) CH3 – CH – CH2 – CH3
CH3 NO2
OH
(1) I > II > III (2) III > I > II
OH
(3) II > III > I (4) I > III > II
(3) CH3 – C – CH3
42. When phenol is treated with CHCl3 and NaOH, the
product formed is CH3
(1) Benzaldehyde (2) Salicylaldehyde (4) CH 3 CH CH2

3. In the given reaction
(3) Salicylic acid (4) Benzoic acid
HI
43. The compound which does not react with sodium, is C6H5 O CH2 CH3 (A) + (B).
(1) CH3COOH (2) CH3 – CHOH – CH3 Product (A) and (B) will be
(1) C6H5–OH and CH3–CH2–I
(3) C2H5OH (4) CH3 – O – CH3
(2) C6H5–I and C2H5OH
44. Reaction of CH2 – CH2 with RMgX leads to formation (3) C6H5–I and C2H5I
O
(4) C6H5–OH and C2H4
of
4. The order of reactivity of the following alcohols
(1) RCH2CH2OH (2) RCHOHCH3 towards HCl is
R CH3
CHCH2OH CH3 F
(3) RCHOHR (4)
R
F OH OH
45. Which of the following will not be soluble in sodium I II
hydrogen carbonate?
(1) 2,4,6-trinitrophenol Ph OH
(2) Benzoic acid OH
IV
(3) o-Nitrophenol III
(1) III > IV > II > I (2) IV > II > III > I
(4) Benzenesulphonic acid (3) IV > III > II > I (4) II > III > I > IV
5. Decreasing order of boiling points amongst the 12. The end product of the reaction is
following follows the order
HNO2 PCl5 NH3
Ethyl amine A B C
(A) Butanol-1
(1) Ethyl amide (2) Ethyl amine
(B) Butanol-2
(C) 2-methyl-2-propanol (3) Acetamide (4) Methyl amine
(1) A > B > C (2) B > A > C 13. Glycerol reacts with KHSO4 to produce
(3) C > A > B (4) C > B > A (1) Trinitro glycerine (2) Acrolein
6. Acidic strength is maximum for (3) Glyceraldehyde (4) Formic acid

(1) o-amino phenol 14. HBr reacts fastest with
(2) m-amino phenol (1) 2-methyl propan-2-ol (2) Propan-2-ol
(3) p-amino phenol (3) Propanol (4) 2-methyl propan-1-ol
(4) All have equal Ka 15. Phenol reacts with CCl4 in excess of NaOH will
7. Phenol can be distinguished from alcohol produce
(1) Tollens reagent (2) Schiff’s base (1) Picric acid (2) Salicylaldehyde
(3) Neutral FeCl3 (4) Fehling solution (3) Salicylic acid (4) Benzoic acid
8. Intermediate formed when phenol reacts with 16. Increasing rate of reaction in a base catalyzed
chloroform in the presence of base is hydrolysis reaction is
(1) CCl2 (2) CCl3 O

Me Me H O Me
(3) CCl4 (4) CHCl3
9. Which one of the following alcohols will give E1 Me Me Me H
reaction most readily? (B)
(A)
(1) CH 3 CH2 OH H O H Et O Et
(2) CH 3 CH2 CH2 OH
H H Et Et
CH3
(C) (D)
(3) CH3 C CH2 CH2 CH2OH (1) (C) < (B) < (A) < (D)
CH3 (2) (B) < (A) < (D) < (C)

(3) (D) < (A) < (B) < (C)
CH3
(4) (D) < (C) < (B) < (A)
(4) CH3 C CH2OH
OH
CH3 
H /
17. (P)
O (Major)
HO OH
10. The reaction of with RMgX followed by
Which of the following statements is correct for the
hydrolysis will produce formation of above product?
(1) RCH2CH2OH (2) RCH(OH)CH3 (1) The reaction proceeds through formation of
carbocation
(3) RCH(OH)R (4) RCH2CH2R
11. Order of reactivity of HX towards ROH is (2) The major product is benzene
(1) HI > HBr > HCl (2) HCl > HBr > HI (3) The major product is an aromatic compound
(3) HBr > HCl > HI (4) HBr > HI > HCl (4) All of these
18. In Victor Meyer's test, red colour is given by (1) 2-methylcyclohexan-1-ol
(2) 2-methylcyclohexane-2-ol
(1) (2) OH
OH
(3) 1-methylcyclohex-1-ol
(3) OH (4) OH (4) 1-methylcyclohexen-1-ol
24. The acidic strength of methoxyphenols are in order

OH
O O
(1) Para > Ortho > Meta > Phenol
(1) CO2, NaOH CH3–C–O–C–CH 3
19. (A) (B)
(2) H (2) Para > Ortho > Phenol > Meta
(3) Meta > Phenol > Ortho > Para

Product (B) is
O (4) Meta > Phenol > Para > Ortho
OH O–C–Me O–H
H
CHO COOH 25. P
(1) (2) CH = CH2
P is
OMe OH O
CH3
COOH C–OCH3
(3) (4) (1)
O
20. The treatment of methanol with ethylmagnesium

iodide liberates a gas at STP. The gas is (2)
O CH3
(1) CH4 (2) CH3CH3
O
(3) CH3OH (4) CH 3 – CH – OH (3) CH3 – C
CH3
O O
(4)
/ 373K
21. + HI P
O (excess) 26. Which of the following option is incorrect?
Product P of the reaction (1) Sodium may be used to dry diethyl ether and
not ethanol
(1) (2) (2) Anhydrous CaCl2 cannot be used for drying

HO I I I
ethanol containing traces of water
(3) Williamson synthesis is not superior method

(3) (4) No reaction
OH OH for preparation of ether
22. Cyclopentene is best prepared from cyclopentanol (4) An ether fire is not extinguished by water
by using
27. t-butyl alcohol and phenol can be distinguished by
(1) Conc. H3PO4 (2) Conc. HCl/ZnCl2
(1) Lucas test
(3) Conc. HBr (4) Conc. HI
(2) Neutral FeCl3 test
1. Hydroboration
23. CH3  P (3) Both (1) & (2)
2. Oxidation
P is (4) Sodium bicarbonate test
ONa 31. Which of the following option is true for below

Allyl chloride , 250C
conversion?
28.  X 
P  Q
Cl Reaction (1) Reaction (2) Reaction (3)
What is the name of enclosed reaction and major
product P? NaOH; 623 K CHCl3 D3O+
300 atm A B C
NaOH; 340 K
O–H
CH2 – CH = CH2
(1) Fries rearrangement; (1) Reaction (1) is called Dow’s process
(2) B is phenol and formed via activated
O–H
nucleophilic substitution
CH2 – CH = CH2
(2) Claisen rearrangement;
(3) B is sodium salt of salicyclic acid
(4) C is acetyl salicyclic acid
O–H
(i) BH3, THF
32. (ii) H2O2, OH
– X
(3) Claisen rearrangement;
Identify X.
CH2 – CH = CH2
O–H CH3
(1)
(4) Fries rearrangement;
OH
CH2 – CH = CH2 OH
O–H
(2)
29. NaNO2 H2SO4
 P CH3
CH3
Product P may be
(3) OH
O–H O–H
OH
(1) (2)
CH3
N=O NO2 (4)
O
(1) X
(3) (4) Both (1) & (3) 33. CH3 – CH – CH = CH2 (2) Y CH3 – CH – CH2CHO
CH3 CH3
N – OH
Here X and Y are
O–H
Ni HI (1) B2H6/H2O2/OH– and PCC/CH2Cl2
30. 3H2  X  Y
Re d P
(2) H2O/H+ and CrO3
Product Y is (3) B2H6 and PCC
O
(4) PCC/CH2Cl2 and B2H6/H2O2/OH–
(1) (2) 34. The reagent(s) used for the determination of
number of hydroxyl groups is/are
O
(1) (CH3CO)2)O (2) CH3COCl
(3) (4)
(3) CH3COOC2H5 (4) Both (1) and (2)
38. Ethylene oxide when treated with Grignard reagent
(i) B2H6 H2SO4
35. CH3CH–CH=CH2 – X Y yields
(ii) H2O2/OH 140°
CH3 (1) Primary alcohol
(2) Secondary alcohol

What is Y?
(3) Tertiary alcohol
(1) CH3–CH–CH2–CH2–O–CH2–CH2–CH–CH3
(4) Cyclopropyl alcohol
CH3 CH3
O
(2) CH3–CH–CH=CH2
Mg/ dry ether (i) CH3–C–CH3
CH3 39. Cl Br (1 eq.) A B
(ii) H3O+
(3) CH3–CH–CH–O–CH–CH–CH3
What is B?
CH3 CH3 CH3 CH3
CH3 CH3 OH
(4) CH3–C–O–C–CH3 (1) Cl C–CH3
C2H5 C2H5 CH3

NaOH
36. + H2SO4 (fuming) X 570-620K Y
OH OH
What is Y?
(2) CH3–C C–CH3
OH SO3H
CH3 CH3
(1) (2)
ONa OH
(3) CH3–C Br
(3) (4)
CH3
(1) Mg Br2
37. CH CH CH2 Br A B (4)
2 (2) HCHO CCl4
+
(3) H3O KOH
C H 2SO 4 Sn + HCl
40. + HNO3 X Y
Product (C) is
NaNO2 + HCl H 2O
(1) Z A . What is A?
0-5°C
O
.. NH2 NO2
(2)
O
..
(1) (2)
CH 2 CH CH2 C H2 OH
(3)
OH OH
OH
HO
(4) (3) (4)
HO O
44. Which of the following is the correct ease of

CH2OH dehydration?
+ H2SO4 A OH
41.
170°C
(conc.) CH3–CH2–CH2–CH2 CH3–CH2–CH–CH3
OH
What is the major product A? I II
OH OH
CH2 CH3
CH2=CH–CH–CH3
III
(1) (2) IV
(1) I > III > II > IV (2) IV > III > II > I
CH3
(3) IV > II > III > I (4) III > IV > II > I
(3) (4) 
H3O
A
45. CH3 – C = CH2 (1) B2H6 /THF
H

Br2/Fe B
42. + CH3–CH2–CH2–OH A B CH3 (2) H2O2 /OH

Product A and B can be distinguished by

What is the major product B?
(1) Sodium metal
CH2–CH2–CH3
(1) (2) Neutral FeCl3
(3) Lucas reagent
(2) CH 3–CH–CH 2 (4) Esterification reaction
Br Br
CH3
CH3 Al2O3/ HBr
46. CH3 – C – OH A B
CH3–C–Br CH3–O–O–CH3
CH3 MgBr
(3)
aq. NaOH
D C
CH3
The end product D of the reaction is
CH3–CH
O – C(CH3)3
(4) (1)
Br (CH 3) 3 – C – CH 2
(2)
43. Which of the following is the correct increasing order
of boiling point of following compounds?
(3)
CH3–CH2–CH2–OH CH3–CH–CH3 CH3–O–CH2–CH3
OH OH
I II III Br Br
(1) II < I < III (2) III < II < I (4)
(3) I < II < III (4) II < III < I Br
47. Consider the following reaction : Cl
Zn dust CH Cl D D
Phenol  X  3
Anhydrous AlCl
Y
3
(2)
Alkaline KMnO4 D D
  Z
H2O/H D
The product Z is Cl
(1) Benzene (2) Toluene T T
(3) Benzaldehyde (4) Benzoic acid (3)

T T
OH OH OH T
48. CH2–CH–CH2 + HI X (4) All are equally reactive
(excess)
52. Among the following four compounds
What is X?
a. Phenol
I I I I
b. Methyl phenol
(1) CH2–CH–CH2 (2) CH2=CH–CH2
c. Meta nitrophenol
(3) CH3–CH=CH2 (4) CH3–CH–CH3
d. Para nitrophenol
I The acidity order is
49. OH (1) d > c > a > b
red P Br2 (2) c > d > a > b

+ HI X h
Y
(1 eq.) (3) a > d > c > b
CH2OH (4) b > a > c > d
What is Y? 53. H .
OH CH3
I C OH
Br
SOCl2
(1) (2) Product (major)
Pyridine
CH2Br CH2I The product is

OH Cl H
CH3 CH3
C H C Cl
(3) (4)
(1) (2)
CH2Br CH2Br
50. Which of the following will not give positive test with
(3) Mixture of (1) & (2) (4) No reaction
neutral FeCl3?
(1) Nitrophenol (2) Phenol CH2
(3) Allyl alcohol (4) o-cresol 54. HCl aq KOH conc. H2SO4
1 eqv.
A B C (major)
51. In Dow's process haloarene is converted to phenol
with fused NaOH. The most reactive compound is Product (C) is
Cl CH3 CH2
H H (1) (2)
(1)
H H
(3) (4)
H
55. Reaction of t-butyl bromide with sodium methoxide

produces (1) (2) O
(1) Sodium t-butoxide O O OH
(2) t-butyl methyl ether OH

(3) O (4)
(3) Isobutane O
OH
(4) Isobutylene
HI/ alc. KOH/ Cl2/h
O 59. excess A B C
CH3 CH3MgBr Cu
56. C CH2 + A B O
H3O 300ºC
CH3
Product C is
B is
(1) Alkyl iodide
(1) (CH3)3CHO
(2) Vinyl chloride
(2) CH3 – C = CH – CH3
(3) Vinyl iodide
CH3
(4) Allyl chloride
(3) (CH3)2CHCOCH3
OH
(4) CH3C – CH2 – CH2CH3
SO3H
O 60. aq. Br2
excess A (Major)
57. Ethyl chloride is converted into diethyl ether by
(1) Perkin’s reaction A is
Br OH
(2) Grignard reaction
SO3H Br
(3) Wurtz synthesis (1) (2)
(4) Williamson’s synthesis
58. OH OH
CH3 CH CH2
Br SO 3H Br Br
PCl5 Mg O
 A ether B + C
H3O
O CH 2OH (3) (4)
Product (C) is Br Br
  

Alcohols, Phenols and Ethers

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Alcohols, Phenols and Ethers

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Chapter 17

Alcohols, Phenols and Ethers

(i) Compounds Containing C  OH bond :

Ex. : CH3OH : Methyl alcohol

CH3 – CH – OH : Isopropyl alcohol

ALCOHOLS AND PHENOLS

Major product comes from more stable intermediate.

BH3 RCH CH2

2. From hydrolysis of alkyl halides :

3. From carbonyl compounds :

Here If R1 R2 H, alcohol will be RCH2 — OH (1° alcohol)

Solution : (i) : butan-2-ol

It involves benzyne mechanism.

CH3 CH3 CH3 CH3

Example 2 : Arrange the following as mentioned

(increasing order of boiling points)

(b) (i) OH (ii) HO OH (iii) HO (iv) HO

(increasing order of solubility in water)

(1) Acidity of alcohols and phenols:

Alcohols are, however weaker acids than water

O–H O–H O–H O–H O–H

Phenoxide ion is also resonance stabilised

Compound Formula pKa

o-Nitrophenol o-O2 N–C6H4–OH 7.2

m-Nitrophenol m-O 2N–C6 H4 –OH 8.3

Phenol C6H 5–OH 10.0

o -Cresol o-CH3 –C6 H4 –OH 10.2

m-Cresol m-CH3–C6H 4–OH 10.1

p -Cresol p-CH3 –C6 H4 –OH 10.2

Ethanol C2H 5OH 15.9

Example 3 : Arrange the following in decreasing order of acidic nature of

—NO2 is stabilizing O– by strong electron withdrawing nature, — CH3 is destabilizing by

Reactions involving R O bond cleavage :

This reaction is given by alcohols only.

CH3CH2OH + HBr  CH3CH2Br + H2O

(ii) Reaction with PCl3 and PCl5 :

Secondary and tertiary alcohols are dehydrated under milder conditions.

Step II : Formation of carbocation

Step III : Formation of ethene by elimination of a proton

To drive the equilibrium to the right, ethene is removed as it is formed.

For this conversion any of the following reagent can be used:

(i) KMnO4/ OH– /  followed by hydrolysis

(iv) Conc. HNO3

(PCC). N + HCl + CrO3

Secondary alcohols are oxidised to ketones by CrO3.

(1) Sec-butyl alcohol (2) Tert-butyl alcohol

(3) Iso-butyl alcohol (4) n-butyl alcohol

Cl2 /H2O aq. KOH

(1) 2-chloroethanol (2) 2-chloromethanol

(3) 1-chloroethanol (4) Ethylene glycol

5. 3-methyl-1-butene on oxymercuration-demercuration yields _______ as the major product.

(1) 3-methyl-2-butanol (2) 2-methyl-2-butanol

(3) 3-methyl-1-butanol (4) 2-methyl-1-butanol

6. What is Z in the following sequence of reactions?

(1) CH3CH2CH2OH (2) CH3CHOHCH3

(3) (CH3CH2)2CHOH (4) CH3 – CH = CH2

7. Which of the following is the strongest base?

(1) tert-butoxide (2) Ethoxide

(3) iso-propoxide (4) Methoxide

(1) 1-pentanol (2) 2-pentanol