5 Organic Compounds Containing

Oxygen I

Topics Covered

1. Classification of Alcohols
2. Nomenclature of Alcohols
3. Isomerism in Alcohols
4. General Methods of Preparation
5. Physical Properties of Alcohols
6. Reactions Involving the Cleavage of O–H Bond
7. Reactions Involving the Alcohol Molecule
8. Reactions Involving the Cleavage of R–O Bond
9. Distinction between Primary, Secondary, and Tertiary Alcohols
10. Preparation and Properties of Ethylene Glycol
11. Preparation and Properties of Glycerol
12. Phenol
13. Nomenclature of Phenol
14. Preparation of Phenol
15. Physical Properties of Phenol
16. Chemical Properties of Phenol
17. Acidic Nature
18. Electrophilic Aromatic Substitution Reaction in Phenols
19. Reimer–Tiemann Reaction, and Kolbe’s Reaction
20. Coupling Reaction of Phenols
21. Fries Rearrangement
22. Condensation Reactions of Phenols
23. Introduction to Ethers
24. Nomenclature of Ethers
25. Isomerism in Ethers
26. Methods for the Preparation of Ethers
27. Physical Properties of Ethers
28. Chemical Properties of Ethers: Reaction with Halogen Acids

Alcohols
Alcohols are compounds obtained by replacing one or more hydrogen atoms in the molecule of alkane
with the hydroxyl (OH) group.

Organic Compounds Containing Oxygen – I 285

 —H
R—H R—OH
Hydrocarbon + OH Alcohol

Classification of Alcohols
Alcohols are classified as monohydric, dihydric, trihydric, and polyhydric according to the number of
one, two, three, or many hydroxyl groups present in the molecule.
CH2 — OH

CH3 CH2 OH CH2 OH CH — OH

Ethyl alcohol CH2 OH CH2 — OH
(Monohydric) Ethylene glycol
Glycerol
(Dihydric) (Trihydric)

Do You Know?

Alcohols containing more than one hydroxyl group attached to the same carbon atom are highly
unstable and lose water molecules to form a more stable aldehyde or ketone.

OH

CH3 — CH — OH CH3 — CH = O + H2O

Classification of Monohydric Alcohols

Monohydric alcohols are further classified as primary (1°), secondary (2°), and tertiary (3°) according to
the OH group attached to primary, secondary and tertiary carbon atoms, respectively.
H H CH3

CH3 C OH CH3 C OH CH3 C OH

H CH3 CH3

Ethyl alcohol Isopropyl alcohol tert-Butyl alcohol

(1° alcohol) (2° alcohol) (3° alcohol)

Nomenclature of Alcohols
Monohydric alcohols are represented by the general formula CnH2n 1  OH . Generally, three systems of
nomenclature are used for naming monohydric alcohols.
1. Common system
In this system, alcohols are named by adding the word alcohol to the name of the alkyl radical pres-
ent in the molecule, e.g.,
CH3

OH CH3 C OH

CH3 CH2 CH CH3 CH3

CH3CH2OH
Ethyl alcohol Sec-butyl alcohol tert-Butyl alcohol

286 Organic Compounds Containing Oxygen – I

2. Carbinol system
The simplest monohydric alcohol, CH3OH , is called carbinol. All other members are considered its
alkyl derivatives.

CH3

OH CH3 — C — OH

CH3 CH2 OH CH3 CH CH3 CH3

Methyl carbinol Dimethyl carbinol Trimethyl carbinol

3. IUPAC system
According to this system, the alcohols are called alkanols, i.e., by replacing –e from the name of
alkane by –ol, i.e.,
Alkane –e + ol = Alkanol.
For the branched chain molecules, the longest chain containing the functional group is selected.
The numbering is done from one end in such a manner that the carbon atom carrying the OH group
gets the lowest number. The position of the substituents is then indicated by suitable numbers.

Example 1: Give the IUPAC names of the following compounds.

OH CH3

(A) CH3 CH2 CH CH3 (B) CH3 — CH — CH2 — CH2 — OH

CH3
OH

(C) CH3 C OH (D)

CH3

(E) CH3 — CH — CH = CH2

OH

Solution: (A) Butan-2-ol

(B) 3-methylbutan-1-ol
(C) 2-methylpropan-2-ol
(D) Cyclohexanol
(E) But-3-en-2-ol
In the IUPAC system, dihydric alcohols are named alkanediols and trihydric alcohols are named
alkanethiols.

CH2OH CH2OH

CH2OH CH OH

Ethane–1,2–diol CH2OH
Propane–1,2,3-triol

Organic Compounds Containing Oxygen – I 287

 Isomerism in Alcohols
Alcohols exhibit various types of isomerism, as discussed below.
1. Chain isomerism
Chain isomerism exists due to differences in the structure of the chain.
CH3 CH2 CH2 CH2 OH CH3
CH CH2OH
Butan-1-ol
1-ol
CH3

2–methylpropan-1-ol
ylpropan-1-ol

2. Position isomerism
This isomerism is due to the difference in the position of the hydroxyl group.
CH3 CH2 CH2 OH CH3 CH CH3

e. g., Propan–1–ol
n–1–ol OH
Propan–2–o
–2–ol
–2–o

3. Functional isomerism
Saturated monohydric alcohols show functional isomerism with ethers e.g.,
CH3CH2OH CH3 — O — CH3

Ethanol
nol Methoxymethan
ethane
ethan

4. Optical isomerism
It is shown by alcohols having at least one chiral carbon (C*)
CH3 CH3

H — C*— OH HO — C*— H

C2H5 C2H5

Non-superimposable mirror images of each other.

General Methods of Preparation of alcohol

1. By hydrolysis of haloalkanes with aqueous alkali or moist silver oxide

R – X + KOH (aq)
q) R – OH + KX
Alcohol

R – I + AgOH ROH + AgI

2. By the reaction of aldehydes, ketones, and esters with Grignard reagents

Grignard reagents react with aldehydes, ketones, and esters to form addition compounds which, on
hydrolysis with dilute acid yield the corresponding alcohols.

δ+ δ– δ– δ+ OMgX
Dryy
C O + R — MgX C OH
ethe
et her
he H+ H2O OH
R C + Mg
Aldehyde Gr
Grignard R X
or Addition
reagent
reagen Alcohol
Ketone Product
Produc

288 Organic Compounds Containing Oxygen – I

 a. Primary alcohol
 Primary alcohols are obtained when the Grignard reagent is reacted with oxygen, or formalde-
hyde or ethylene oxide.

H2O OH
1
RMg X + O ROMg X ROH + Mg
2 2 X
The alcohol has the same carbon atoms as present in the alkyl group of the Grignard reagent.

H H OMgBr
Dry
C O + C2H5MgBr C
H ether C2H5
H

H OH OH
H+ H2O
C + Mg
H C2H5 Br

Propan–1–ol
The alcohol has one carbon atom more than the alkyl group of the Grignard reagent.

CH2
O + C2H5MgBr C2H5CH2 CH2OMgBr
CH2
Ethylene oxide
+
H2O/H OH
C2H5CH2 CH2OH + Mg
Br
The alcohol has two carbon atoms more than the alkyl group of the Grignard reagent.
b. Secondary alcohol
With aldehydes other than formaldehyde, secondary alcohols are obtained.

CH3 CH3 OMgI

Dry ether
C O + CH3MgI C
H H CH3

H+ / H2O CH3 OH OH
C + Mg
H I
CH3
Propan–2–ol
 econdary alcohols can also be prepared by the addition of a suitable Grignard reagent to esters
S
of formic acid, followed by acid hydrolysis.

OMgBr
δ– δ+
H δ+ δ– CH3 — MgBr
C O H C OC2H5
H5C2O
CH3

Organic Compounds Containing Oxygen – I 289

 OC2H5
— Mg O
Br + CH3 MgBr
H C CH3

OMgBr OH
OH
H+ / HO
H2
H C CH3 H C CH3 + Mg
Br
CH3 CH3
Propan–2–ol
c. Tertiary alcohol
With ketones, tertiary alcohols are obtained.

CH3 CH3 OMgBr

Dry ether
C O + CH3MgBr C
CH3 CH3 CH3

CH3 OH OH
H+ / HO
H2
C + Mg
CH3 CH3 Br

2-methylpropan-2-ol
Tertiary alcohols can also be easily prepared by the addition of Grignard reagent to an ester other
than a formic ester, followed by acid hydrolysis.

CH3 CH3 OMgBr

C = O + CH3 MgBr C
H5C2O H5C2O CH3

O
+ CH3Mg Br
— C2H5 OMgBr
CH3 — C — CH3

OMgBr OH
OH
H+ / HO
H2
CH3 C CH3 CH3 C CH3 + Mg
Br
CH3 CH3

3. By hydrolysis of esters

H+
RCOOR '+ HOH 
HOH  
RRCOOH
COOH + R ' O
OH
H+
RCOOR '+ HOH 
HOH  
RRCOOH
COOH + R ' O
OH

290 Organic Compounds Containing Oxygen – I

4. By reduction of carbonyl compounds, including acid derivatives
A number of reducing agents like Na/C2H5OH, LiAlH4, NaBH4, and hydrogen in presence of a catalyst,
such as Ni, Pt or Pd can be used.
R — CHO + 2H R — CH2 OH
Aldehyde 1° alcohol

R R
C O + 2H CHOH
R′ R′
Ketone
2° alcohol

R — C — OH + 4H R — CH2OH + H2O
Acid 1° alcohol

R — C — OR' + 4H R — CH2OH + R

Ester

Do You Know?

The reduction of aldehydes, ketones and esters with sodium and alcohol is commonly known as
Bouveault-Blanc reduction.

Do You Know?

Esters cannot be reduced to the corresponding alcohols either catalytically (i.e., H2/Ni or Pt or Pd)
or by NaBH4 .

5. By the action of nitrous acid on primary aliphatic amines

Primary alcohols are formed when primary amines are treated with nitrous acid.
R N H2
+
R OH + N2 + H2O
HO N O

C2 H5 NH2 + HONO C2H5OH + N2 + H2O

Rack Your Brain

Can we prepare secondary and tertiary alcohols by this method?

Organic Compounds Containing Oxygen – I 291

 6. By hydration of alkenes
Alkenes are passed through concentrated H2SO4 to form alkyl hydrogen sulphates. These upon
hydrolysis with boiling water give alcohols.
CH2 CH3 H2O CH3
+ H2SO4 + H2SO4
CH2 CH2HSO4 Boil CH2OH
Ethene Ethyl hydrogen Ethyl
sulphate alcohol

Do You Know?

Except for ethyl alcohol, no other primary alcohol can be prepared by this method as the addition
of H2SO4 follows Markownikoff ’s rule.

Alkenes may also be catalytically hydrated in dilute acids, and addition takes place in accordance
with Markownikoff ’s rule.

OH
H+
CH3 — C = CH2 + H2O CH3 — C — CH3

CH3
CH3

Do You Know?

The major product for the following reaction is shown below.

CH3
H+
CH3 — CH — CH = CH2 + H2O
?
CH3 CH3
H+ +
CH3 — CH — CH = CH2 CH3 — C — CH — CH3
2° Carbocatio
rbocation
rbocatio
H

1, 2 hydride shif
ift
if

CH3 CH3
OH –
CH3 — C — CH2CH3 CH3 — C — CH2 — CH3
+
3° Carbocatio
rbocatio
rbocation
OH
(Major product)
duct)

292 Organic Compounds Containing Oxygen – I

 The alkenes needed for the purpose are obtained on a large scale by cracking of petroleum. Indirect
addition of water to alkenes can also be carried out by the following two methods.
a. Oxymercuration–demercuration
The net result of the reaction is the hydration of an unsymmetrical alkene in accordance with
the Markownikoff’s rule.
(CH3COO)2 Ag
R — CH = CH2 R — CH — CH2
THF / H2O
OH Hg OOCH3

NaBH4

R — CH — CH3

OH
b. Hydroboration–oxidation
The net result of the reaction is the addition of water to alkenes according to anti-Markownikoff’s rule.
Dry ether H2O2
1
3R — CH = CH2 + BH (RCH 2 CH )
2 3 B 3 RCH2CH2 OH
2 2 6 NaOH
7. Oxo process
Alkenes react with carbon monoxide and hydrogen in presence of cobalt carbonyl as catalyst, under
high temperature and pressure to form aldehydes. These upon catalytic reduction give primary
alcohols.
[Co (CO)4]2 H2 / Ni
CH2 = CH2 + CO + H2 CH3CH2CHO CH3 CH2 CH2OH
High temp,
pressure
8. Fermentation of carbohydrates
Alcohols can be prepared by the fermentation of carbohydrates under the influence of suitable
enzymes.
Invertase
C1 2H22O 1 1 + H2O C6H1 2O6 + C6H1 2O6
(In yeast)
Glucose Fructose
Maltase
C1 2H22O1 1 2 C6 H12 O6
in yeast
glucose
C6H12O6  2 C2H5OH  2 CO2
Zymase
In yeast
Glu cos e

Physical Properties of Alcohols

1. Lower members of alcohols are colourless liquids with a characteristic alcoholic smell and burning
taste. The higher members are colourless, odourless waxy solids.

Do You Know?

Methanol is also called ‘wood spirit’ since originally, it was obtained by the destructive distillation of wood.

2. Boiling points of alcohols are higher than those of alkanes, haloalkanes or ethers of comparable
molecular masses. This is because, in alcohols, intermolecular hydrogen bonding exists, due to
which a large amount of energy is required to break these bonds.

Organic Compounds Containing Oxygen – I 293

 R R R
δ+ δ+ δ+
O —H O —H O —H
δ– δ– δ–
Hydrogen bonding
Energy is required to overcome the attractive forces resulting from hydrogen bonding. As a result,
their boiling points are higher than the corresponding hydrocarbon, ethers or alkyl halide, which do
not form hydrogen bonds. Among isomeric alcohols, the boiling points are in the following order
Primary > Secondary > Tertiary

3. Solubility lower alcohols are highly soluble in water, but solubility decreases with the mass of the
alcohol. The solubility of alcohols in water is due to the formation of hydrogen bonds between
alcohol and water molecules.
δ+ δ– δ+ δ– δ+ δ–
H—O H—O H—O

R H R
As the molecular mass increases, the hydrocarbon part (i.e, alkyl group) becomes larger, which
resists the formation of hydrogen bonds with water molecules, and hence, the solubility goes on
decreasing. Among isomeric alcohols, the solubility increases with branching. This is due to the
reason that as the branching increases, the surface area of the hydrocarbon part decreases and the
solubility increases.

Do You Know?

Alcohols cannot be dried over anhydrous CaCl2 or MgCl2 as they form solid derivatives called alcoholates.
CaCl 2  4CH3OH  Cal 2 . 4 CH3OH

MgCl 2  6C2H5OH  MgCl 2 . 6C2H5OH

Chemical Properties of Alcohols

The chemical properties of alcohols are mainly of the hydroxyl group, which has a polar character due
to the electronegativity difference between oxygen and hydrogen atoms. The chemical reactions are
divided into the following classes, as shown below.
1. Reactions involving the cleavage of RO H bond
2. Reactions involving the cleavage of R OH bond
3. Reactions of alcohol molecule as a whole.
1. Reactions involving the cleavage of RO H bond
The general order of reactivity of alcohols towards this type of reaction is

H H R R
>

>

H—C —O—H > R > C—O—H > R > C —O —H > R > C—O—H
>

H H H R
Methanol Primary Secondary Tertiary

Explanation: in the reactions involving the cleavage of the O–H bond, the oxygen atom is to take up
the electron pair from the bond. The presence of the alkyl group with the +I effect tends to increase

294 Organic Compounds Containing Oxygen – I

 the electron density around oxygen atom. Consequently, the bond cleavage in O–H bond becomes
difficult. This adversely affects the reactivity of alcohol. Greater the number of alkyl groups present
in alcohol, lesser will be its reactivity.
A few important reactions involving the cleavage of O–H bond are discussed below.
a. Weakly acidic nature
Alcohols are weakly acidic in nature and do not turn blue litmus red. However, they evolve hy-
drogen with active metals like sodium, potassium, magnesium, and aluminium.
2 ROH + 2M 2 R — O– M+ + H2
Where (M = Na, K, Mg, Al, etc.)
The weakly acidic character of alcohols is due to the +I effect of the alkyl group, which makes
the release of H+ ions from O–H bond quite difficult. Moreover, there is no resonance in either
alcohol or alkoxide ion, which is left after the release of the H+ ion. This also makes the release
of the H+ ion quite difficult.
.. ... –
.. — H
R—O ...
R —O + H+
No resonance No resonance

Do You Know?

Finkelstein halogen exchange reaction is suitable mainly for iodides and fluorides.

Alcohols are even less acidic than water because, in water (H – O–H), there is no alkyl group with
the +I effect. As a result, the release of H+ ions from the H2O molecule is easier than from the
molecule of ROH.
Alcohols react with metal hydrides to form alkoxides and evolve hydrogen gas.
R — O — H + M+H– R — OM + H2
Metal alkoxide
Alkoxides are extensively employed for the preparation of ethers on treatment with an alkyl halide.
(Williamson’s synthesis)

RONa + R X R — O — R + NaX
Ether
The acidic character of alcohols is also represented in the following reactions.
OR
ROH + R′ Mg X R′ — H + Mg
X s
ROH + Na+ –C CH RONa + HC CH

Do You Know?

Finkelstein halogen exchange reaction is suitable mainly for iodides and fluorides.

What would be the order of acidity among H2O, ROH, HC ≡ CH, NH3, and RH?
b. Reaction with carboxylic acids (esterification)
Alcohols react with organic acids to form esters. The process is known as esterification.

Organic Compounds Containing Oxygen – I 295

 O O
H2SO 4
R — C — OH + H OR′ R — C — OR′ + H2O

O O
H2SO4
CH3 — C — OH + HOCH2 CH3 CH3 — C — OCH2 CH3 + H2O

Do You Know?

The reaction is reversible in nature and the equilibrium can be shifted to the right by removing
water as soon as it is formed.

The order of reactivity of alcohols follows the order

CH3OH > CH3CH2OH > (CH3 )2 CHOH > (CH3 )3 COH
And that of carboxylic acids follows the order
HCOOH > CH3COOH > (CH3 )2 CHCOOH > (CH3 )3 CCOOH
This order of reactivity is due to the steric hindrance of the alkyl group attached to the alcoholic
or the carboxyl group.
Mechanism of esterification involves the nucleophilic attack of the alcohol on the protonated
acid and proceeds as follows.
..
.. .. :OH
O O R' O
.. H+ .. H .. H
R—C R —C R — C — OH
..
O OH
.. H
R' — O
.. — H
+
OH
H+ shift
R — C — OH
+ ..
.. : OH
O OH
–H+ –H2O +
R —C R—C R — C — OH2

OR' OR' OR'

Ester

Do You Know?

In the esterification reaction, the OH part of the carboxyl group and the H atom of alcohol is
removed as water. This has been confirmed with the help of isotopic labelling, e.g., when benzoic
acid is esterified with methyl alcohol containing O–18 oxygen (labelled alcohol), the labelled oxygen
after the reaction is present in the ester and not in water.

O O
H+
C6H5 — C — OH + CH3O18H C6H5 — C — O18CH3 + H2O

296 Organic Compounds Containing Oxygen – I

 c. Reaction with an acid chloride or acid anhydride (Acylation)

O O O O

R — C — O — C — R + H OR ′ R — C — OR ′ + R — C — OH

O O

R — C — Cl + H OR ′ R — C — OR ′ + HCl
This reaction is called acylation. If the acid halide and anhydride used are acetyl chloride and
acetic anhydride, respectively, the reaction is usually termed acetylation. However, if benzoyl
chloride is used, the reaction is called benzoylation.
The acetylation of alcohols is usually carried out in the presence of a base, such as pyridine or
dimethylaniline.
O O
Py
CH3 — C — Cl + H O C2H5 CH3 — C — OC2H5

Rack Your Brain

The yield of the ester is better in acylation reaction as compared to the esterification reaction
carried with a carboxylic reaction.

Mechanism
The mechanism involves the nucleophilic attack of alcohol on acid chloride or acid anhydride
molecule.
..
.. : O :–
O: .. +
..
R—C + : O — R' R — C — O — R'
Cl
H Cl H
O O
–
– Cl +
.. ..
R — C — O — R' –H+
R — C — ..O — R'

H
Protonated ester Ester

2. Reactions involving the cleavage of the R–OH bond

In these reactions, the order of reactivity of alcohols is 3° > 2° > 1°
R R H H

R C — OH > R C — OH > R C — OH > H — C — OH

R H H H

Explanation: the alkyl group with the +I effect tends to increase the electron density towards the
carbon atom, as well as, the oxygen atom. Both the carbon and oxygen atoms tend to acquire partial
negative charge (δ–). Due to repulsion between the atoms, the C–O bond gets elongated and its
cleavage becomes quite easy. Thus, the greater the number of alkyl groups present, the greater will
be reactivity of alcohol.

Organic Compounds Containing Oxygen – I 297

 a. Reaction with halogen acids
ROH + HX RX + H2O

Order of reactivity of various halogen halides is

HI > HBr > HCl
Order of reactivity of various alcohols is
3° > 2° > 1°
HCl/ZnC 2l
R — Cl + H2O
48% HBrr
R — OH R — Br + H2O
or NaBr + Conc H2SO4
57% HI R — I + H2O
Or KI + H3PO4

Both HBr and HI do not exist, as such and are prepared in the reaction mixture (in situ).
The mixture of concentrated HCl and anhydrous ZnCl2 is called the Lucas reagent. THe Lucas
reagent can be used to make distinction between 1°, 2°, and 3° alcohols.

ZnCl
Cl2
CH3CH2CH2CH2OH + HCl CH3CH2CH2CH2Cl+ H2O
∆
White turbidity
y
(At room temp, no reacti
tion)
ti

ZnCl
Cl2
CH3CH2CH CH3 + HCl CH CH CHCH3 + H2O
room temp 3 2
OH Cl
White turbidit
Whit idity
y
(Within 1–2 minute
tes)
te

CH3
OH
ZnCl
Cl2 CH3 — C — CH3 + H2O
CH3 — C — CH3 + HCl
room temp
mp
CH3 Cl
White turbidit
ity
it
(Immediately))

Mechanism
For 2° and 3° alcohols, the the SN1 mechanism is proposed.
+ –
R — OH + HX RO H2 + X
+
R — OH2 R+ + H2O

R+ + X − → R − X
Primary alcohols react through the SN2 mechanism.
+ –
R — OH + HX R — OH2 + X
+
δ– δ+
: X – + R – OH2 X R OH2 X — R + H2O

In the case of alcohols reacting through the SN1 mechanism, the alkyl group may undergo
rearrangement due to rearrangement in the intermediate carbocation.

298 Organic Compounds Containing Oxygen – I

 Rack Your Brain

What would be the product of the following reaction?

CH3 H
HCl
CH3 — C — C — CH3 ?

H OH

b. Reaction with Phosphorus halides

R — OH + PCl5 R — Cl + POCl3 + HCl
3 R — OH + PCl3 3 R — Cl + H3PO 3

c. Reaction with Thionyl chloride (SOCl2)

R — OH + SOCl2 R — Cl + SO2 + HCl

Do You Know?

Finkelstein halogen exchange reaction is suitable mainly for iodides and fluorides.

This is the best method for the preparation of alkyl chloride because the by-products of SO2 and
HCl are gases which can be easily removed, leaving behind pure RCl.
d. Reaction with ammonia
Al2 O 3
R — OH + NH3 R — NH2 + H2O
250°C
3. Reactions involving alcohol molecule as a whole
a. Dehydration
Alcohols undergo dehydration to form alkenes (removal of a molecule of water) on heating them
with a protonic acid, e.g., concentrated H3PO4 or catalyst, such as anhydrous zinc chloride or alu-
mina.

Acid
—C—C— C=C + H2O
Heat
H OH
The order of ease of dehydration of alcohols is: 3° > 2° > 1°; this may be illustrated by the fol-
lowing reactions.
95% H2SO4
CH3CH2OH CH2 CH2
170°C
60% H2SO4
CH3CH2CH — CH3 CH3CH CHCH3
100°C
OH Chief product
Sec-Butyl alcohol 2–Butene
alcohol

Organic Compounds Containing Oxygen – I 299

 CH3 CH3
20% H2SO4
CH3 — C — CH3 CH3 — C CH2
85–90°C
OH
Isobutylene
tert-Bulyl alcohol
The dehydration of alcohol follows the E1 pathway.
Mechanism:
The mechanism of this reaction involves protonation of alcohol followed by loss of water mole-
cule and a proton.

—C—C— + H:B —C—C + B (Protonation)

H OH H OH2
+

—C—C— — C — C — + H2O (Loss of H2O)

+
H + OH2 H

— C — C — + H2O C C + H:B (Loss of proton)

+
H

B:
In all cases, intermediate is a carbonium ion and there may be rearrangement (1, 2-hydride or 1,
2-methyl shift) to form a more stable carbocation.
The orientation of the product strongly follows the Saytzeff rule, i.e., when more than one alk-
ene can be formed, the preferred product is the more stable one.

Do You Know?

Dehydration is reversible.

Rack Your Brain

What would be the product of the following reaction?

H+
CH3CH2CH2CH2OH ?
Heat

Alcohols leading to conjugated alkenes are dehydrated to a greater extent than those of alco-
hols leading to non-conjugated alkenes. Thus, dehydration is in order.

> >
OH OH

OH

300 Organic Compounds Containing Oxygen – I

 Rack Your Brain

Which will be dehydrated at a faster rate?

CH2 CH — CH — CH3 or CH3 — CH2 — CH — CH3

OH OH

b. Action of hot copper

Primary and secondary alcohols are dehydrogenated to yield aldehydes and ketones, respec-
tively, whereas tertiary alcohols are dehydrated to form alkenes.
Primary Alcohol Secondary Alcohol Tertiary Alcohol

CH3 CH3
CH3 CH2 OH
CH OH
Cu, 573 K CH3 Cu, 573 K CH3 — C — OH
CH3 CH = O + H2
CH3 CH3
C O + H2
CH3 Cu, 57
Cu 573 K

CH3 — C = CH2

CH3 + H2O

Table 5.1
Thus, this method can be used to make distinction between 1°, 2°, and 3° alcohols.
c. Oxidation
The oxidation of alcohols can be carried out with a variety of reagents, such as neutral, acidic
or alkaline KMnO4, acidified K2Cr
Cr2O7 or dilute HNO3 .
Aqueous KMnO4 or K2Cr Cr2O7 oxidises 1° alcohol to an acid having the same number of carbon
atoms as in alcohol.
– +
RCH2OH + KMnO4 RCOO K + MnO2 + KOH
H
1° alcoho
cohol
coho Purple
rple Brown
n
H+

RCOOH
A carboxylic acid
2–
RCH2OH + Cr2O7 RCHO + Cr 3+

Orange
e Green
n

RCOOH
Secondary alcohols are oxidised to ketones with the same number of carbon atoms as the orig-
inal alcohols.
R K2Cr2O7 or R
CH OH C O
R Cr 3
CrO R

Organic Compounds Containing Oxygen – I 301

 Oxidation of ketones takes place only under vigorous conditions and yields carboxylic acids with a
lesser number of carbon atoms than alcohol. The reaction is the oxidative degradation of alcohols.
Tertiary alcohols are not oxidised with mild oxidising agents in an aqueous alkaline or under
neutral conditions. However, when oxidation is carried out under acidic conditions, tertiary alco-
hols first undergo dehydration to form an alkene. The alkene formed is then oxidised to ketone,
which is finally oxidised to a carboxylic acid with a lesser number of carbon atoms than the
starting alcohol.
Based on oxidation products, we can differentiate between 1°, 2°, and 3° alcohols.
Primary Alcohol Secondary Alcohol Tertiary Alcohol
CH3 CH3
CH3 CH2 OH
CH OH
[O] CH3 [O] CH3 — C — OH

CH3
[O]
CH3
CH3
CH3CHO
C=O
CH3 — C = CH2
[O] CH3
[O]] , ∆
[O [O]]
[O

CH3

CH3COOH CH3COOH
OH + CO2 + H2O CH3 — C = O + CO2 + H2O
[O]

CH3 COOH + CO2 + H2O

Table 5.2
Other reagents used for oxidation are shown below.
 
a. PCC (pyridinium chlorochromate C5H5 NHClCr O3 ) to oxidise 1° alcohol to aldehydes and
2° alcohols to ketones.
b. PDC (pyridinium dichromate (C5H5NH)2+
2
(Cr2O72−) to oxidise 1° alcohol to aldehydes and
2° alcohols to ketones.
c. H2CrO
CrO4 (chromic acid) to oxidise 1° alcohols to carboxylic acids.
d. CrO
O3 .H2SO4 acetone to oxidise 2° alcohol to ketones.
e. Jones reagent (chromic acid in aqueous acetone solution) oxidises 1° alcohol to aldehyde and
2° alcohol to ketone without affecting (C = C) double bond.
f. MnO2, selectively oxidises the OH group of allylic and benzylic 1° and 2° alcohols to give
aldehydes and ketones, respectively.
H OH O

CrO3 / H2SO4

–
KMnO
nO4 /OH (cold)

OH
O
OH O
[O]

OH O

302 Organic Compounds Containing Oxygen – I

 d. Action of halogens
Chlorine and bromine being mild oxidising agents, oxidise 1° and 2° alcohols to aldehydes and
ketones, respectively. The oxidation products are halogenated at α − carbon atom in the pres-
ence of excess halogens.
Cl2
CH3CH2OH + Cl2 – CH3CHO CCll3 CHO
2HCl Excess
Chlora
ral
ra
CH3 CH3 Cl2 CCll3
CHOH + Cl2 C O C O
CH3 CH3 CCll3

Trichloroacetone
ne

Distinction between Primary, Secondary and Tertiary Alcohols

The three classes of alcohols can be distinguished from one another by the following tests.
1. Lucas test
2. Action of hot copper
3. Oxidation
4. Victor-Meyer test: this test consists of the following steps.

Primary Alcohol Secondary Alcohol Tertiary Alcohol

RCH2OH R R3C — OH
CHOH
CHO
P + I2 R P + I2
P + I2

R
RCH2 — I CH — I R 3C — I
R
AgNO2 AgNO
NO2
AgNO 2

R R3C — NO2
RCH2 — NO2 CH — NO 2
R HNO2
HNO2 HNO2

No reaction
RC — NO2 R
C — NO2 NaOH
NOH R
N=O Colourless
Nitrolic acid Pseudonitrol
NaOH
NaOH

Blood red colouration Blue colouration

Table 5.3

Iodoform test: all alcohols of the structure R — C — CH3 (R = H, alkyl or aryl group) on treatment with

OH
iodine and sodium hydroxide, yield a yellow precipitate of iodoform. (CHI3)

Organic Compounds Containing Oxygen – I 303

 ∆
CH3 — CH — R + 4X2 + 6 NaOH
OH CHX3 + RCOONa + 5 H2O + 5 NaX
X

OH
All 2-alkanols respond to the haloform test.

Do You Know?

Ethyl alcohol CH3CH2OH is the only primary alcohol which gives the iodoform test.

Rack Your Brain

Which of the following will give a positive iodoform test?

CH3 — CH — CH3 , CH3 CH2 CH2OH, CH3 — CH — CH2 — CH3

OH OH

Some Commercially Important Alcohols

Ethane –1, 2 diol (Ethylene glycol)
Method of preparation
a. From ethene
nO4 | OH–
dil. KMnO
CH2 — CH2
Cold
OsO4 / HO
H2 2 OH OH
CH2 = CH2
CH2 — CH2 (Syn addition)
OH
OH OH
RCOOOH H₂O / H⁺
CH2 — CH2 CH2 — CH2
CH2— CH2 (Anti addition)
O OH

HOCl
Cl NaHCO3
CH2 — CH2 CH2 — CH2 + NaCl + CO2

OH Cl OH OH
b. From ethylenediamine
CH2 NH2 CH2OH
+ 2HNO2 + 2H2O + 2N2
CH2 NH2 CH2OH

Physical Properties
Ethylene glycol is a colourless viscous liquid with a high boiling point (470 K). It is highly soluble in water
and ethanol but is insoluble in ether. The high solubility in water is due to extensive intermolecular
hydrogen bonding.

304 Organic Compounds Containing Oxygen – I

 Do You Know?

Ethylene glycol forms low freezing mixtures with water and is therefore, used as antifreeze.

Chemical Properties
1. Reaction with sodium
CH2OH CH2ONa
Na, 50°C
°C

CH2OH CH2OH

Na, 160°C
C

CH2ONa

CH2ONa

2. Reaction with PCl5

CH2OH CH2Cl
+ 2 PCll5 + 2POCll3 + 2HCl
Cl
CH2OH CH2Cl

3. Reaction with SOCl2

CH2OH CH2Cl
+ 2SOCll2 + 2SO2 + 2 HC
HCll
CH2OH CH2Cl

4. Reaction with PCl3, PBr3, PI3

PBr3 CH2Br

CH2Br

CH2OH CH2Cl
PCll3
CH2OH CH2Cl

CH2I –I2 CH2

PI3
CH2I CH2
Unstable

5. Reaction with Nitric acid

CH2OH CH2ONO2
Conc. H2SO4
+ 2HNO3 + 2H 2O
CH2OH CH2ONO2
Ethylene Glycol
Dinitrate

Organic Compounds Containing Oxygen – I 305

 6. Reaction with Monocarboxylic acid
CH2OH CH2O — COCH 3
CH3COOH / H + COOH/H+
CH3CO
CH2OOCCH3

CH2OH CH2OH CH2OOCCH3

Glycol
Glycol diaceta
tate

7. Reaction with Dicarboxylic acids

Glycols form polyesters on condensation with dicarboxylic acids.

CH2OH
COOH
n + n(CH 2 )x
HOCH2 [CH2OOC(CH2)x CO
COOCH2]nCH2OH
CH2OH COOH

8. Dehydration
Under different conditions, ethylene glycol undergoes dehydration in different ways.
CH2OH
775 K
CH2 — CH2 + H2O
CH2OH O

CH2OH CH2 CH3

ZnCl
Cl2 / ∆ Tautomerises
omerises

–H2O CHOH CHO

CH2OH

Unstable
able
O
CH2OH CH2
Conc. CH2SO 4 / ∆ CH2
2
+ 2 H2O
CH2OH CH2 CH2

O
Dioxane

CH2OH HOCH2 CH2 OH

H3PO 4 /
2
+ H2O
CH2OH CH2 O CH2
Diethylene gl
glycol
ycol

9. Oxidation
a. Ethylene glycol on oxidation with concentrated HNO3 mainly gives glycollic acid and oxalic acid.
The other oxidation products, such as glyoxal and glyoxalic acid are also formed in small
quantities because they are more readily oxidised than glycol itself.

306 Organic Compounds Containing Oxygen – I

 CH2OH [O] CHO COOH
[O]

CH2OH CH2OH CH2OH

Ethylene glyco
glycol Glycoaldehyde Glycolic acid

[O] [O]

CHO [O] COOH [O] COOH

OH

CHO CHO COOH

Glyoxall Glyoxalic acid Oxalic acid

b. When ethylene glycol is treated with periodic acid (HIO4) or lead tetraacetate carbon-carbon
bond fission occurs to give formaldehyde.
CH2OH
+ HIO4 2 HCHO + H2O + HIO3
CH2OH
CH2OH
+ (CH3COO)4 Pb 2 HCHO + 2 CH3COOH + (CH3COO)2Pb
CH2OH

Do You Know?

Periodic acid (HIO4) and lead tetraacetate are specific for 1, 2-glycol splitting, i.e., they can oxidise
1, 2 glycols but not 1, 3-or higher glycols, therefore these reagents are used to determine the
structure of polyhydroxy compounds.
HIO 4
CH2 — CH2 — CH2 No reac
reacti
tion
or (CH3COO)4Pb
OH OH

c. When acidified KMnO4 or acidified K2Cr2O7 is used, carbon-carbon bonds undergo cleavage and
formic acid is formed,
CH2OH KMnO4
2HCOOH + H2O
CH2OH
10. Reaction with aldehydes and ketones
When heated with aldehydes and ketones in the presence of p-toluenesulfonic acid (PTS) as a
catalyst, ethylene glycol gives cyclic acetals and cyclic ketals (1, 3-dioxolanes)
CH2OH H CH2O H
PTS , ∆ C
+ O C + H2O
CH2OH R CH2O R

CH2OH R1 CH2O R1
PTS, ∆ C
+ O C + H2O
CH2OH R2 CH2O R2

These acetals and ketals are widely used for protecting a carboxyl group in polyfunctional com-
pounds where the reactions are desired at the other functional group in basic media. After the

Organic Compounds Containing Oxygen – I 307

 desired reaction, the carbonyl group may be regenerated by the addition of periodic acid to an
aqueous solution of the dioxolane or by acidic hydrolysis.
R O — CH2 HIO4
C RCOR + 2HCHO
R O — CH2
+
H3O

R
C O + CH2OH
R
CH2OH

The Pinacol Pinacolone Rearrangement

R1 R3 R1
H+
R2— C — C — R 4 R2 — C — C — R4

OH OH O R3

R = Alkyl, aryl, or hydrogen

When vicinal diol (glycols) are treated with acids, they can be rearranged to give aldehydes or ketones.
This reaction is called the pinacol rearrangement; the reaction gets its name from the typical compound
pinacol, which is rearranged to pinacolone.

CH3 CH3 CH3

+
H
H3C — C — C — CH3 H3C — C — C — CH3

OH OH O CH3

2,3-dimethyl-2-3-
3-dimethyl-2-3-butan
3-dimethyl-2-3- butaned
butanedio
ioll 3,3-dimethyl-2-
3, 3-dimethyl-2- butanone
butano
(Pinacol) (Pinacolone)
(Pinacolone

The mechanism involves a simple 1, 2 shift.

CH3 CH3 CH3 CH3 CH3 CH3

+
H
H3C — C — C — CH3 H3C — C — C — CH3 H3C — C — C — CH3
–H2 O
+
OH OH OH OH2 OH
+
CH3 CH3
1,2-Me Shift + +
H
H3C — C — C — CH3 H3C — C — C — CH3

OH CH3 O CH3
However, when different groups are present on C-atoms bearing the hydroxyl groups, two questions
arise.
1. Which of the two OH’s will be protonated and
2. Which of the groups will migrate.

The answer to the first question lies with the stability order of carbocation. Usually that OH receives the
proton, which produces the more stable carbocation by the elimination of water molecules.
Thus, in Ph2COH.COHMe2 the OH group on the C atom holding the phenyl groups, will receive the
proton since the stability of diphenyl carbocation is greater than that of dimethyl carbocation. As we

308 Organic Compounds Containing Oxygen – I

know, carbocation stability is enhanced by a group in the order aryl > alkyl > hydrogen and this normally
determines, which side loses the OH group. However, exceptions are known and, which group is lost may
depend on the reaction conditions, as well as, nature of substrate, e.g.,

Ph Me Me
HOAc
Ph — C — C — Me Ph — C — C — Me
trace of H2SO 4
OH OH O Ph

Cold H2 S
SO
O4

Ph

Me — C — C — Ph

O Me
There is no clear-cut answer so far as migratory preference is concerned. More often than not migratory
aptitudes are in the order aryl > alkyl, but exceptions are known and the position of hydrogen in this
series is often unpredictable.

Propane 1, 2, 3-triol (glycerol or glycerine)

Methods of preparation
1. By saponification of oils and fats
CH2OCOR CH2OH

CHOCOR + 3 NaOH CHOH + 3 R COONa

a

CH2OCOR CH2OH Sodium salt of fatty

y acids
acid
(soap)
Oil or fat Gl erol
Glyc ol

2. From propene
CH3 CH2Cl CH2OH CH2OH CH2OH

Cl2 aq Na2CO 3 HOCl aq NaOH

CH CH CH CH Cl CHOH
770 K 423 K, 12 atm
m
CH2 CH2 CH2 CH2OH CH2OH

Physical Properties
It is a colourless, odourless, viscous, and hygroscopic liquid with a sweet taste. It is soluble in water in
all proportions. It has high boiling point, i.e., 290°C. The high viscosity and high boiling point of glycerol
are due to association through hydrogen bonding.

Chemical Properties
1. Reaction with sodium only 1° alcoholic group is attacked.
CH2OH CH2ONa CH2ONa

Room temp
mp Na
CHOH + Na CHOH CHOH
High temp

CH2OH CH2OH CH2ONa

Organic Compounds Containing Oxygen – I 309

 2. Reaction with PCl5, PBr3 and PI3
CH2OH CH2Cl

CHOH + 3PCl 5 CHCl + 3 POCl + 3HCl

HCl
3

CH2OH CH2Cl

Glyceryl trichlorid
oride
orid
CH2OH CH2Br

CHOH + PBr3 CHBr + H PO

3 3

CH2OH CH2Br

CH2OH CH2I CH2

CHOH + PI3 CHI CH + I2

CH2OH CH2I CH2I

Unstable ally
allyll Allyl
All yl io
iodide
dide
3. Reaction with HCl or HBr
CH2OH CH2Cl CH2OH CH2Cl CH2Cl

110°C Ex
Excess of HCl
CHOH CHOH + CHCl CHCl + CHOH
OH
+ HCl 110°C
110°
CH2OH CH2OH CH2OH CH2OH CH2Cl

Glycerol
Glycero Glycerol Glycerol Glycerol
α-mono- β-mono- -dichloro α, α′ -dichloro
α, β-dichlor
chlorohydrin chlorohydrin hydrin hydrin

Similarly it reacts with HBr.

4. Reaction with HI
When heated with a small amount of HI, allyl iodide is the main product. However, on heating with
an excess of hydrogen iodide, the product obtained is isopropyl iodide.
CH2OH CH2I CH2 CH3 CH3 CH3
HI (excess) HI
or HI CH CHI
CHOH CHI CH CHI
– I2 – I2

CH2OH CH2I CH2I CH2I CH2 CH3

Allyl iodide Isopropyl iodide

5. Reaction with nitric acid
CH2OH CH2ONO 2

H2SO 4 (Conc.)
CHOH + 3 HNO3 CHONO 2 + 3H2O

CH2OH CH2ONO 2

Glyceryl trinitrate
nitroglycerin
(Noble's oil)

310 Organic Compounds Containing Oxygen – I

 Do You Know?

A mixture of glyceryl trinitrate and glyceryl dinitrate absorbed on kieselguhr is called dynamite.

6. Dehydration
CH2OH CH2

KHSO4
CHOH CH + 2H2O


CH2OH CHO
7. Oxidation
CHO COOH COOH

[O] [O]
CHOH CHOH CHOH
CH2OH
[O]
CH2OH CH2OH COOH
CHOH
Glyceraldehyde Glyceric acid Tartronic acid

CH2OH [O] CH2OH COOH

[O] C=O
C=O

CH2OH COOH

Dihydroxy Mesoxalic acid

acetone

a. With dilute HNO3, a mixture of glyceric acid and tartonic acid is produced.
b. With concentrated HNO3, mainly glyceric acid, is obtained.
c. With Bismuth nitrate, only mesoxalic acid is formed.
d. Mild oxidising agents like bromine water, sodium hypobromite (Br2/NaOH) and Fenton’s reagent
(H2O2 + FeSO4) give a mixture of glyceraldehyde and dihydroxyacetone. This mixture is called
glycerose.
e. With HIO4, glycerol undergoes oxidative cleavage to give two moles of formaldehyde and one
mole of formic acid.
CH2OH
∆
CHOH + 2HIO4 2HCHO + HCOOH + 2HIO3 + H2O

CH2OH
f. With acidified KMnO4, glycerol gets oxidised to oxalic acid, carbon dioxide, and water
CH2OH
COOH
Acidifie
if d
ifie
CHOH + 6[O] + CO2 + 3HO
3H2
KMnO 4
COOH
CH2OH
Oxalic acid

Organic Compounds Containing Oxygen – I 311

 8. Reaction with acetic acid, acetic anhydride or acetyl chloride
Mono-di-and tri-esters are formed.

CH2OH CH2OCOCH3 CH2OCOCH3 CH2OCOCH3

CH3COOH CH3COOH CH3COOH
CHOH CHOH CHOH CHOCOCH3
Or CH3COCl Or CH3COCl Or CH3COCl
CH2OH CH2OH CH2OCOCH3 CH2OCOCH3

9. Reaction with oxalic acid

a. At 110° C and with excess of oxalic acid formic acid is formed.

CH2OH CH2 — OOC COOH CH2OOCH

— CH2OH

CHOH + HOOC — COOH 110°C CHOH Heat

CHOH
H2O
CHOH + HCOOH
– H2O – CO 2
Formic acid
CH2OH CH2OH CH2OH CH2OH
Gl erol
Glycer mono oxalat
alate
alat
ate Glycerol
Glycerol
ol
monoformate
b. At 260° C, allyl alcohol is formed.

CH2OH CH2 — OOC CH2

COOH
260°C Heat
CHOH + CH — OOC CH
– 2CO
O2
COOH
CH2OH CH2OH CH2OH

Glycerol
erol dioxalat
dioxalate
(Dioxalin) Allyl alcohol
alcoho

Phenol
Phenol is the hydroxy derivative of aromatic hydrocarbons in which the hydroxyl group is directly attached
to the carbon atom of the aromatic ring. Phenols are classified as monohydric, dihydric, trihydric, and
polyhydric phenols. Accordingly, their molecules contain one, two, three or many hydroxy groups.

OH OH OH
OH OH

OH
Phenol Catechol Pyrogalloll
(Monohydric) (Dihydric) (Trihydric))
It may be noted that the aromatic compounds in which the –OH group is not directly attached to the
benzene ring are not phenols but are called aromatic alcohols.
CH2OH CH2CH2OH

Phenyl methanol 2-Phenyl ethanol

312 Organic Compounds Containing Oxygen – I

Nomenclature of Phenols
1. Common system: in the common system, the simplest member of this family is called phenol. All
substituted phenols are named as derivatives of phenols. The position of the substituents on the
aromatic ring with respect to the –OH group is indicated by prefixes ortho (O) for 1, 2, meta (m) for
1, 3 and para (p–) for 1, 4.
2. IUPAC system: all substituted phenols are named as derivatives of phenol. Here, the position of the
substituents with respect to the –OH group is indicated by Arabic numerals.
The common and the IUPAC names of some phenols are given below.
OH OH OH
O 2N NO 2

Cl
NO2
Phenol 3-Chlorophenol 2, 4, 6 trinitrophenol
(Picric acid)
Methyl phenols are known as cresols.

OH OH OH
CH3

CH3
CH3

2-methyl phenol 3-methyl

yl phenol 4-methyl phenol
or or or
O-cresol m-cresol p-cresol

OH OH OH
OH

OH
OH

1, 2- dihydroxy 1,3-dihydroxy
3-dihydroxy 1,4-dihydroxyy
benzene benzene benzene
(Catechol) (Resorcinol) (Qui
(Quinol)
ui nol)

OH OH OH
OH OH

OH HO OH
OH
1,2,3-trihydroxy
roxy 1,2, 4-trihydroxy
ihydroxy 1,3, 5-
5-Trihydroxy
benzene benzene benzene
(Pyrogallol) (Hydroxyquinol)
nol) (Phloroglucino
(Phlorog lucinol)
lucino l)

Phenol containing a carbonyl group, such as aldehydic, ketonic, carboxyl, or an ester group is named
as hydroxy derivatives of the parent aromatic compound.

Organic Compounds Containing Oxygen – I 313

 OH OH
CHO COOH

2-Hydroxybenzaldehyde
dehyde 2-Hydroxybenzoic ic acid
ac
(Salicylaldehyde) (Salicylic acid)

OH OH

COOCH3
COCH3
Methyl-3-hydroxybenzoate
4-Hydroxyacetophenon
one
on

Methods of Preparation of Phenols

1. Alkali fusion of sulphonates: sodium salts of sulphonic acids on fusion with NaOH at 573 K followed
by acidification yields phenols.

– +
SO 3Na O Na OH

300°C
300 HCl
+ 2NaOH
–Na2SO 3, – H2O –NaC
aCl

2. Hydrolysis of diazonium salts

+ –
N2 Cl OH

Dil H2SO 4
+ H2O + HCl + N2
∆

3. By decarboxylation of salicylic acid

OH ONa
COONa
CaO
+ 2 NaOH + Na2CO 3 + H2O
Heat

ONa OH

+ HCl + NaCl

4. From Grignard reagent

MgBr OMgBr OH
+ OH
Dr ethe
Dry et r H2O/H
O/
+ 1/2 O2 + Mg
Br

314 Organic Compounds Containing Oxygen – I

Industrial Preparation of Phenol
1. From aryl halides (Dow’s process)
– +
Cl ONa OH

623 K, 300 atm

m HCl
+ 2NaOH
– NaCl, – HO
H2 – NaCl

2. From Cumene

CH3 CH3

H3C — C — H H3C — C — OOH

AlCl
Cl3 Aerial
+ CH3CH 2CH 2Cl Oxidatio
at n
atio
(Cumene) +
H2O/H
O/

OH
O

+ CH3 — C — CH3

3. From coal tar: phenols and cresols are isolated from the middle oil fraction of the coal tar distillation.

Physical Properties of Phenols

1. Phenols are colourless crystalline solids or liquids. However, they become coloured due to slow ox-
idation with air.
2. Phenols boils at higher temperature than the aromatic hydrocarbons of comparable molecular
masses, e.g., boiling point of phenol is 455 K, while that of toluene is 384 K. The higher boiling point
is due to the presence of intermolecular hydrogen bonding in phenols.

δ– δ+ δ– δ+ δ– δ+ δ– δ+
O—H O—H O—H O—H

3. Phenols are sparingly soluble in water. Actually, they form only negligible hydrogen bonding with water,
since the size of the phenyl group is quite large, and it almost masks the polar character of the O—H
group. Phenols are readily soluble in organic solvents like alcohol and ether.

Chemical Properties of Phenols

Phenols contain the –OH group, and thus, resembles aliphatic alcohols in many respects. Apart from
similarities phenol behaves differently from alcohols in many respects due to the presence of benzene ring.
1. Phenol does not undergo elimination reaction to form olefins.
2. Phenol does not undergo reaction involving the cleavage of C–OH bond or substitution of the –OH
group.
3. Phenol does not undergo oxidation in the same manner as alcohols but forms complex products.

Organic Compounds Containing Oxygen – I 315

 1. Reactions due to phenolic (–OH) group
a. Acidic nature
i. Reaction with metallic sodium
OH ONa

+ Na + 1/2 H2

Phenol
henol Sodium
phenoxide
e

ii. Reaction with alkali

– +
OH ONa

+ NaOH + H2O

iii. Phenols turn blue litmus red

Phenols are Stronger Acids than Alcohols

This can be explained by considering relative stabilities of reactants and products in the
ionisation of phenol and alcohol.
Phenol
.. .. .. .. ..
:O — H +O — H +O — H +O — H :O — H
– –

–
(I) (II) (III
II)) (IV) (V)

Phenoxide ion
.. – .. .. .. .. –
:O : :O :O :O :O :

– –

–
(VI) (VII) (VIII) (IX) (X)

A careful study of the contributing structures shows that structures II to IV for phenol have
both positive, as well as, negative charges while in case of phenoxide ion, the structures VII
to IX have only negative charge. Since energy has to be supplied to separate the opposite
charges, these contributing structures for phenol should be more energetic, and less stable as
compared to the structures for the phenoxide ion listed above. As a result, the hybrid of phenol
is less stable and readily changes to the more stable phenoxide ion by releasing the proton
and behave as fairly strong acid. On the other hand, in the case of alcohols neither alcohol nor
alkoxide is stabilised by resonance, and hence, they behave as weaker acid than phenols.
.. ..–
R—O
.. — H .. : + H
R —O

316 Organic Compounds Containing Oxygen – I

 Large resonance
stabilisation

r y
tal energ
rg
– +
RO + H

– +
ti
t nti
Small resonance ArO + H
te
Pote
stabilisation
ROH ArOH

Progress of reaction
The above arguments are also supported by the value of dissociation constant of phenol
(Ka = 10–10) and alcohol (Ka = 10–16 – 10–18).

Rack Your Brain

What would be the order of acidity for phenol, alcohol, and water?

Effect of Substituents on the Acidity of Phenols

Presence of electron withdrawing groups like –NO2, –X, –CN, –CHO, –COOH, etc., which stabilise
the phenoxide ion by dispersing the negative charge relative to phenol increase the acidic strength
of phenols.
-
OH O

+
H + -

G G

G withdraws electrons, stabilises ion, increases acidity

The effect however, is more pronounced at the o- and p- positions than at m-position with
respect to the –OH group. Thus, acidic strength of nitrophenols decreases in the order as
given below.
p-nitrophenol > o-nitrophenol > m-nitrophenol > Phenol.
Further, greater the number of electron-withdrawing groups at o- and p-positions, more acidic
is the phenol.
Presence of electron releasing groups like –NH2, –OR (alkoxy), –R(alkyl), etc., which destabilise
the phenoxide ion by intensifying the negative charge relative to phenol tend to decrease the
acidic strength of phenols.
δ-
OH O

H+ + δ-

G
G
G releases electrons, destabilises ion, decreases acidity.
The effect however, is more pronounced at o– and p-position than at m-position with respect
to the OH group. Thus, the acidic strength of cresols decreases in the order as given below.
Phenol > m-cresol > p-cresol > o-cresol. However, m-methoxy phenol and m-amino phenols are stronger
acids than the phenol because of presence of –I effect and absence of +R effect. Thus, order of acidity is
m-methoxyphenol > phenol > o-methoxy phenol > p-methoxy Phenol.

Organic Compounds Containing Oxygen – I 317

 b. Action of ferric chloride
Phenols form coloured iron complexes when treated with neutral FeCl3 solution. The formation
of the iron complexes is attributed to the existence of keto-enol tautomerism in phenols. Phenol
predominantly exists in enolic form hence, colour formation is used to identify phenols.
OH O

enol keto
OH
3–

6 + FeCl3 + + Fe O
3H + 3HCl
6
enol
In general, all compounds containing the enolic group respond to this test. However, the
colour of complexes are different, such as green or blue or violet, and depend upon the struc-
ture of phenols.
c. Action with zinc dust
OH

+ Zn heat + ZnO
ZnO

d. Reaction of phenoxides with alkyl halides

O Na+
OH –

+ NaOH + H2O

– +
O Na OCH 3

+ CH3I + NaI

Similarly
– +
O Na O — CH2 — CH = CH2

+ Br — CH2 — CH = CH2 ∆ + NaBr

Alkyl phenyl ethers also can be prepared by treating phenol with dimethyl sulphate or diethyl
sulphate in presence of NaOH.
OH OCH 3

NaOH, ∆
+ (CH3)2SO 4
–Na
a2SO 4, –H2O

OH OCH 2CH 3

NaOH, ∆
+ (C
(CHH3CH 2 )2 SO4
–Na
a2SO 4, –H2O

318 Organic Compounds Containing Oxygen – I

 e. Action with acid chlorides and acid anhydride (Acylation)
Phenol reacts with acid chloride or acid anhydride to form an ester in excellent yield. The reaction
with acetyl chloride is usually catalysed by a base, such as pyridine, that with acetic anhydride is cat-
alysed both by acids (a few drops of concentrated H2SO4) and bases (sodium acetate, pyridine, etc.).
OH OCOCH3
O
pyridine
+ CH3 — C — Cl + HCll

OH OCOCH3
O O
H2SO4 or
+ CH3 — C — O — C — CH3 + CH3COOH
CH3COONa

f. Action with benzoyl chloride (Benzoylation)

OH OCOC6H5
O
NaOH
+ C6H5 — C — Cl + HCl

Do You Know?

The reaction of phenols with benzoyl chloride in presence of aqueous NaOH to form phenyl benzoate
is called the Schotten-Baumann reaction.

Phenyl esters on heating with anhydrous AlCl3 undergo a rearrangement to yield o- and p-hy-
droxyderivaties of ketones. It is called called the Fries rearrangement. The mechanism of this
reaction is discussed later on in this session.
g. Reaction with Grignard’s reagent
OH OMgI

+ RMgI + RH

h Reaction with PCl5

OH

+ PCll5 Cl + POCl3 + HCl

Do You Know?

Yield of C6H5Cl in above reaction is small due to formation of triphenyl phosphate.

i. Reaction with ammonia

OH NH2

573 K
+ NH3 + H2O
ZnCl2

Organic Compounds Containing Oxygen – I 319

 2. Electrophilic aromatic substitution reaction in phenols
In phenols, the –OH group activates the benzene ring towards electrophilic substitution reaction
and directs the substitution at ortho and para positions.

O—H +O — H +O — H +O — H O—H
–
–

δ+
OH

δ– δ– +
E (ele
(electrophile) can attack
at oo and p– positions.
δ–

a. Halogenation: phenols when treated with aqueous solution of halogens undergo halogenation
rapidly to form polyhalogen derivatives.
OH OH

Br Br
H2O + 3 HBrr
+ 3Brr2

Br
2, 4, 6–Tribromop
ribromopne
nenol
ne
(white ppt))
Phenols are so reactive towards bromine water that even substituents like –SO3, –NO2, etc., if
present at o- and p-position may be replaced.
OH OH
Br Br
+ 3Brr2 (aq.) + 3HBr + H2S
SO4

SO 3H Br
If halogenation is carried out in a solvent of low polarity, such as chloroform or carbon disul-
phide, reaction can be limited to monohalogenation.
OH OH OH

Br
Br2,CS2
+
0°C

Br
(Chief
ef product)
t)
In aqueous solution, phenol ionises to form phenoxide ion. Due to the presence of negative
charge, the oxygen of the phenoxide ion donates electrons to the benzene ring to a large extent.
As a result, the ring gets highly activated, and hence, trisubstitution occurs. On the other hand,
in non-polar solvents, the ionisation of phenol is greatly suppressed. Consequently, the ring is
slightly activated, and hence, only monosubstitution occurs. Further, because of steric hindrance
at the ortho position, the para substitution product usually predominates.

320 Organic Compounds Containing Oxygen – I

 b. Sulphonation
OH
SO 3H
15 - 20°C
OH

H2SO 4 H2SO 4, 100°C

OH

100°C

SO 3H
c. Nitration
With dilute nitric acid phenol gives a mixture of o- and p-nitrophenols and the yield is poor due
to partial oxidation of the ring by HNO3.
OH OH OH

Br
Br2,CS2
+
0°C

Br
(Chief product
product)

Do You Know?

The ortho and para isomers can be easily separated by steam distillation as o-nitrophenol is
steam volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to
intermolecular hydrogen bonding, which causes the association of molecules.
O O
N H

O
O
O
HO N
O HO N
O
o-nitrophenol
henol
p-nitropheno
henol
heno

With concentrated nitric acid phenol gives 2, 4, 6 trinitrophenol (picric acid). The yield is poor
since most of the phenol is oxidised by concentrated nitric acid.

OH OH

O 2N NO 2
Conc.HNO 3
Conc.H2SO 4

NO 2
However, ring can be deactivated by sulphonation and then nitration will give picric acid in better
yield.

Organic Compounds Containing Oxygen – I 321

 OH OH OH
SO 3H O 2N NO 2
+ H2SO 4 HNO 3

SO 3H NO 2
2,4,6-trinitrophenol
(Picric acid)
d. Nitrosation:
Phenols react with nitrous acid (NaNO2 and HCl) to form p-nitrosophenol and this gets oxidised
to p-nitrophenol with dilute nitric acid as follows.
OH OH OH

HNO 2 Dil. HNO 3

280 K (Oxidation)

NO NO2

p-nitrosopheno
osophenol
osopheno p-nitrophenol
ol
Thus, indirect nitration of phenol gives a better yield of the product as compared to direct ni-
tration with dilute nitric acid.
e. Friedel-Craft alkylation
OH OH OH
CH3
+ CH3Cl
Anhy
nhydrous + + HCl
AlCl3
AlCl

CH3
2-methyl pheno
henol
heno 4-methyl phenol
4- enol

The yield of the alkyl phenols is generally low since AlCl3 coordinates with, oxygen atom. To avoid
this alkylation it is normally done in the presence of HF or dil-H2SO4.
OH OH
CH3
HF
+ CH3 — C — CH3
Cl
CH3 — C — CH3
CH3
f. Friedel-Crafts acylation
OH OH OH
O
COCH3
AlCl
Cl3
+ CH3 — C — Cl +

COCH3
Although phenolic ketones can be prepared by direct acylation of phenols, they are more often
prepared in two steps by means of Fries rearrangement.
g. Kolbe’s reaction: when sodium phenoxide is heated with CO2 at 400 K and at a pressure of
4-7 atm, sodium salicylate is formed as the major product. This on acidification gives salicylic acid.
ONa OH OH
COONa COOH
400 K H
+
+ CO2
4 - 7 atm
m

322 Organic Compounds Containing Oxygen – I

 It seems likely that CO2 attacks itself initially to phenoxide oxygen rather than to the ring.
O
ONa OCONa OH
COONa
D
+ CO 2

At higher temperature (250 – 300° C), p-isomer is obtained.

Mechanism:
The mechanism of this reaction is believed to involve an electrophilic attack by carbon dioxide
on the highly activated ring.
–
O O OH OH
H –
COO COOH
H+
+ C O C O
O O
Salicylic acid is the starting material for a number of useful chemicals, such as aspirin
(2-acetoxybenzoic acid), which is widely used as analgesic (pain reliever) and antipyretic (to lower
body temperature during fever), salol (phenyl salicylate) as an intestinal antiseptic and oil of winter
green (methyl salicylate), which is used in perfumery and as a flavouring agent in food, drinks, etc.
OCOCH
OCOC H3
COOH
(CH3COO)
O)2O
Conc.H2SO 4 + CH3COOH
OH
Aspirin
OH
OH
COOC6H5
COOH C6H5OH
POCl
Cl3 + H2O
Salol
Sa
OH
CH3OH COOC
CO OCH
H3
Conc. H2SO 4
+ H2O
Oil of winter
nt green
nter
h. Reimer-Tiemann reaction: treatment of a phenol with chloroform in presence of aqueous alkali
introduces an aldehyde group –CHO, onto the aromatic ring, generally ortho to the –OH. This
reaction is called Reimer-Tiemann reaction
OH ONa ONa OH
CHCl
Cl2 CHO CHO
CHCl
Cl3, aq NaOH H2 O +
H
70°C
Salicylald
laldehyde
lald
(Chief prod
product)
If carbon tetrachloride is used in place of chloroform, salicylic acid is obtained as the major product.
OH ONa ONa OH
CCll2 COONa COOH
CCll4, aq NaOH +
H
70°C
Salicylic acid

Organic Compounds Containing Oxygen – I 323

 Mechanism:
The Reimer-Tiemann reaction involves electrophilic substitution on the highly reactive phenoxide ring.
The electrophilic reagent is dichlorocarbene, CCl2, generated from chloroform by the action of base.
– –
OH + CHClCl3 H2O + : CCll3
–
: CCll3 Cl + : CCll2
Dichlorobenzene
.. – –
– O
O :O O
H– CHCl
Cl2 CHO
2 NaOH
+ : CCll2 CCll2

Do You Know?

Although electrically neutral, dichlorocarbene contains a carbon atom with only a sextet of electrons,
and hence, is strongly electrophilic.

Coupling Reaction
Phenols react with diazonium salts in slightly alkaline medium at low temperature to form coloured
compounds called azo dye.
NaOH
OH + N2Cl N=N OH

p-hydrox
dr yazobenzene

Mechanism:
A detailed study of the coupling reaction has shown that the mechanism is electrophilic substitution,
the eletrophile being the diazonium cation, and the substrate being the phenoxide ion.

OH + NaOH O– Na+ + H2O

H
.. + –
N = N + O N=N O

– H+

OH
H+ –
N N N N O

It has been stated that coupling between phenols and diazonium salts take place most rapidly in weakly
alkaline medium (pH 9-10). Under these conditions, the phenol is present mainly as phenoxide ion, which
is a stronger nucleophile than phenol and couples much more easily than phenol.

324 Organic Compounds Containing Oxygen – I

 OH –
O

OH–

H+

Phenol Pnenoxide ion

(Couples slowly
owly)
owly (Couples rapidl
pidly)
pidl

Coupling with benzene substrate occurs preferentially in the p-position to the hydroxyl group but if this
is blocked, then o-coupling occurs, e.g., p-cresol gives the o-azo compound.
OH OH
– OH–
ArN2Cl +

CH3 N = N – Ar
H3C
p–cresol
The presence of another activating group in m-position of the phenol accelerates coupling, e.g., resorcinol
forms the mono-, bis-, and tris azo-compounds more readily than does phenol.
OH OH OH OH
+ – ArN2 N2Ar
ArN2 Cl Ar N2

OH–
OH OH OH
N2Ar N2Ar N2Ar

Fries Rearrangement
When esters of phenols are heated with aluminium chloride, the acyl group migrates from the phenolic
oxygen to an ortho or para position of the ring, thus yielding a ketone. This reaction is called Fries
rearrangement.

OH O
O – C – CH3 OH OH

C – CH3
CH3COCl AlCl 3
+
CS2
o- hydroxy
acetophenone COCH3
CO

p–hydroxy aceto phenone

At low temperature, ortho isomer is formed in excess while at high temperature p-isomer is formed in
excess.
Mechanism:
It is electrophilic in nature and involves the attack of the acylium ion (RCO+). The ion is generated from
phenyl acetate with the help of aluminium chloride (AlCl3). The latter being a Lewis acid complexes with
the ester as follows.

Organic Compounds Containing Oxygen – I 325

 Cl

CH3CO + AlCl 2
CH3CO – O
O O AlCl 2

+
+ AlCl 3
+ CH 3 CO + Cl –

Electrophile attack at the ortho position.

O AlCl2 + OAl
AlCl
Cl2
O AlCl
AlCl2 OH
COCH3
H COCH3
+ – H+ H2O
+ C = O COCH3

CH3
o- hydroxy
acetophenone
Electrophile attack at the para position also.

+
OAlCl
Al 2 OAlCl
Al 2 OAlCl
AlCl 2 OH
CH3

– H+ H2O
+C = O

H COCH3
COCH3 COCH3
p–hydroxy
acetophenone
Gattermann reaction (Formylation)

OH OH

ZnCl
Cl2 CHO
+ HCN + HCl +
H3O

This reaction is used to prepare aldehyde when activating groups like –OH, –NH2 are present.
Mechanism

ZnCl2 + –
HCN + HCl Cl – CH = NH CH = NH + ZnCl3

+
OH OH OH OH
+ H CH = NH CHO
CH = NH H3O+
CH = NH

o–hydroxy
benzaldehyde

326 Organic Compounds Containing Oxygen – I

Reduction OH OH

Ni, 533x
x
+ 3H2

Cyclohexanol
Oxidation OH O OH O

CrO2Cl 2
+ O2 (air)) + H2O + H2O

O O
Quinone

Do You Know?

Phenol is colourless when freshly prepared but when exposed to air it becomes pink due to the
formation of p-benzoquinone.

Phenol is also oxidised by potassium persulphate (K2S2O8) in alkaline medium and gives a mixture of
catechol and p-quinol.
OH OH OH
– OH
K2S2O 8 //OH
+

Catechol
chol OH
Quinol
inol

Condensation with Formaldehyde

When phenol is treated with formaldehyde in the presence of a base or acid acting as catalyst,
a mixture of ortho and para hydroxy benzyl alcohols is formed.

OH OH OH
CH2OH
H+ or OH–
+ HCHO +

CH2OH

These products condense to give a crossed-linked polymer known as Bakelite.

Organic Compounds Containing Oxygen – I 327

 OH OH OH

CH2 CH2 CH2

CH2 CH2

CH2 CH2 CH2

OH OH OH

Do You Know?

This reaction is called Elbs-persulphate oxidation.

Condensation with Pthalic Anhydride

Phenol reacts with phthalic anhydride in presence of concentrated H2SO4 to form phenolphthalein (an
indicator), which gives pink colour with NaOH (Phthalein test of dibasic acid).

O
OH OH

Conc
Conc H2SO4 C
O
– H2O
C
H O H

C
O
C OH OH

O Phenolphthal
halei
ein

Ether
Ethers are compounds of general formula R – O R′.
Ethers may be regarded as dialkyl derivatives of water.

– 2H ..
H –O –H R –O.. – R
+ 2R ether
They may also be regarded as alkyl derivatives of alcohols or anhydrides of alcohols.
–H ..
R –O –H R –O
.. – R
+R

328 Organic Compounds Containing Oxygen – I

 – H2O R
R – OH O
..
R – OH R
When both the alkyl groups are same they are designated as simple or symmetrical ethers and when
both are different, they are called mixed or unsymmetrical ethers.

CH3 – O – CH3 CH3 – O – C2H5

C2H5 – O – C2H5 C6H5 – O – CH3
C6H5 – O – C6H5 C6H5 – O – CH2C6H5
Simple or symmetrical ethers Mixed or unsymmetrical ethers

Ethers are further classified into the following two categories.

1. Aliphatic ethers in which R and R1 are both alkyl groups.
CH3 – O – CH3, CH3 – O – C2H5
Dimethyl ether Ethyl methyl ether
2. Aromatic ethers in which either one or both R and R′ are aryl groups, e.g.,
CH3 – O – C6H5, C6H5 – O – C6H5
Methyl phenyl ether Diphenyl ether

Nomenclature
1. Common system: the common names of ethers are derived by naming the two alkyl or aryl groups
linked to the oxygen atom in alphabetical order and adding the word ether. In case of symmetrical
ethers, the prefix di is used before the name of the alkyl or the aryl group.
CH3

CH3 – O – CH3 CH3 – O – CH – CH3 C 6H 5 – O – C 2H 5

Ethy
hyl phenyl ether
Dimethyl ether Isopropyl methyl et
ether

Some aromatic ethers have their special names.

OCH3 OCH2CH3

Anisole Phenetole
(Methylphenyl ether
her)
her (Ethylphenyl ether)
her)

Cyclic ethers called epoxides or oxiranes have special names.

O O
CH2 – CH2 CH2 – CH2

O CH2 – O

Ethylene oxide Oxetan

Ox etane
etan e Tetrahydrofura
Te ydrofuran
ydrofura Tetrahydropyra
ran
ra

2. IUPAC system: according to IUPAC system, ethers are named as alkoxyalkanes. The larger alkyl
group forms the part of parent chain while lower alkyl group constitute alkoxy radical.

Organic Compounds Containing Oxygen – I 329

 Example: Give the IUPAC names of the following compounds.
(A) CH – O – C H
3 2 5
(B) C2H5 – O – CH – CH2 – CH3

CH3

(C) O CH3 O CH3 (D) OC2H5

CH3 – CH – CH – CH3 CH3 – CH – OC2H5

O CH3 CH3 – CH – CH – CH2 – O C2H5

(E) (F)

Solution: (A) Methoxy ethane

(B) 2-ethoxybutane
(C) 2,3-dimethyoxybutane
(D) 1,1-diethoxyethane
(E) Methoxy benzene
(F) 1-Ethoxy-2-iodo-3-phenylbutane

Isomerism in Ethers
1. Functional isomerism
Ethers are isomeric with alcohols; since both have same general formula CnH2n+2O but different
functional group.
Molecular formula Alcohol Ether
C2H6O CH3CH2OH CH3OCH3
C4H10O CH3CH2CH2CH2OH C2H5 OC2H5
2. Metamerism
Ethers with same molecular formula but different alkyl groups around oxygen are metamers, e.g.,
CH3
C2H5OC2H5 CH3OCH2CH2CH3 CH3 OCH
CH3
Diethyl ether Methyl n-propyl ether Methyl isopropyl ether

Methods of Preparation of Ethers

1. Dehydration of alcohols: ethers are prepared by reactions of the corresponding alcohols with
sulphuric acid.
H2SO4, 180°C
CH2 = CH2
H2SO 4, ∆
2ROH ROR + H2O; CH3CH2OH
H2SO4, 140°C
CH3CH2OCH2CH3

Dehydration of alcohols to ethers rather than to alkenes is controlled by temperature. Ether forma-
tion by dehydration is an example of nucleophilic substitution with alcohol playing two roles; the

330 Organic Compounds Containing Oxygen – I

 protonated alcohol is the substrate and the second molecule of alcohol is the nucleophile. Reaction
could be either SN1 or SN2, depending upon whether the protonated alcohol loses water before or
simultaneously with, or attack by the second alcohol molecule.
R – OH + H+ ROH2+

H
H 2O +
ROH SN1
R R – O – R H+ + R – O – R
+
R – OH2+ H H (3° and 2° alcohol)
ROH + SN2
RO – R H+ + R – O – R
RO R OH2 +
+
+
H2O (1° alcohol)

It is probable that 2° and 3° alcoholes follow the SN1 pattern, whereas, 1° alcoholes follow the SN2
path.

Do You Know?

Dehydration is generally limited to the preparation of symmetrical ethers, because a combination

of two alcohols yields a mixture of three ethers.

Dehydration of lower alcohols can be done by passing the vapours of the alcohol over alumina at
240-260° C.

Al2O3
2C2H5OH C2H5OC2H5 + H2O
240° – 260°C
C

2. Williamsons synthesis: this can be used to make unsymmetrical ethers, as well as, symmetrical
ethers.
In Williamsons synthesis sodium or potassium alkoxide is heated with alkyl halide.

R – X + NaOR' R – O – R' + NaX

Reaction involves nucleophilic substitution of alkoxide ion for halide ion.

R'O – + R – X' R' – O – R + –X

Leaving group
Nucleophile Substrate

For better yield, alkyl halide should be primary and alkoxide should be secondary or tertiary.
CH3 CH3

CH3 – C – ONa + CH3CH2Br CH3 – C – O – CH2CH3 (Feasible)

e)

CH3 CH3

Organic Compounds Containing Oxygen – I 331

 CH3 CH3

CH3CH2ONa + CH3 – C – Cl CH3 – C – O – CH2CH3 (Not Feasible)

e)

CH3 CH3

Secondary and tertiary alkyl halides readily undergo E2 elimination in the presence of strong base
to form alkenes.
CH3 CH3

CH3CH2ONa + CH3 – C – Cl CH3 – C

CH3 CH3

Tendency for alkyl halides to undergo elimination is 3° > 2° >1°.

Similarly, alkyl aryl ethers can be easily prepared by treating sodium phenoxide with alkyl halides.

O Na O CH3

∆ + NaBr
+ CH3Br

Anisole
Anisol

However, anisole cannot be prepared by treating bromobenzene with sodium methoxide.

Br

+ CH3ONa No reaction

This is due to the reason that aryl halides are less reactive towards nucleophilic substitution reac-
tions than alkyl halide. However, strong electron attracting group at ortho or para position increases
reactivity.

aq NaOH
CH2Br + HO NO2 CH2O NO 2

3. By the action of diazomethane on alcohols or phenols

ROH + CH2N2 R – O – CH3 + N2

This reaction always produces methyl alkyl ether.
Mechanism:
HBF4 (strong acid) first protonates CH2N2 to give CH3N2+ from which N2 is lost, ROH acting as nu-
cleophile.

+
–
HBF4 + CH2N2 CH3N2 + BF4

+ +
CH3N2 CH3 + N2

+ +
ROH + CH3 ROCH3 + H

332 Organic Compounds Containing Oxygen – I

4. Addition of alcohols to alkenes
CH3
CH3 CH3OH
C = CH2 CH3 – C – O CH3
H2SO 4
CH3
CH3

Mechanism

+
+
CH2 = CH2 + H CH3 CH2

+ + + –H+
CH3CH2 + ROH CH3CH2 OR CH3 CH2 O R CH3 CH2 O R
Nucleophile
phile
H ; H
As intermediate is carbocation, there can be 1,2-hydride or 1,2-methyl shift to attain greater stability.
5. Alkoxymercuration-demercuration: the method involves addition of alcohol to the alkene to form
ether in accordance with Markownikoff ’s rule.
NaBH
BH4
C C

C = C + ROH + Hg (OOCCF
OCCF3)2 – C – C – RO H
Markownikoff's
's
RO HgOOCCF3 orientation

6. By reaction of alkyl halide with dry silver oxide

∆ C2H5
2 CH3CH2Br + Ag2O (Dry) O + 2AgBrr
C2H5

7. From Grignard reagent

By treating α-haloethers
-haloethers with this reagent higher ethers can be obtained.
I
CH3OCH2Cl + IMg CH3 CH3OCH2CH3 + Mg
Cl

Preparation of Cyclic Ethers (Oxiranes)

1. By reaction of ethylene with oxygen
CH2 Ag CH2
1
+ O2 O
2 200 – 400°C
400°
CH2 CH2

2. By treatment of ethylene chlorohydrin with NaOH

CH2Cl CH2
+ NaOH O + NaCl
Cl + H2O
CH2OH CH2

O–
OH– H – O
– H2O – Cl– O
CH2 – CH2 – Cl
CH2 – CH2 – Cl CH2 – CH2

Organic Compounds Containing Oxygen – I 333

 3. By oxidation of ethylene with peroxy acid like CH3CO3H, C6H5CO3H or CF3CO3H
O
CF3CO 3H
RCH = CHR RCH – CHR
The addition of oxygen to the double bond is an epoxidation reaction and is a syn addition.
CH3 CH3
H3C H H3C H3C H
RCO3H RCO3H H H
H
H3C H O O
H CH3
H H3C

Cis-2-butene
ene Meso - isomer Trans - 2 - butene Pair of enantiome
iomers
iome
Magnesium monoperoxy phthalate (mmpp) can be used instead of peroxy acid because of its stability.
MMPP
O
CH3CH2OH

4. By intramolecular Williamsons reaction

CH2 – CH2 CH2 – CH2
CH2 – CH2
–
–Cl CH2
NaOH
CH2 CH CH2
CH2 CH2 2

Cl O
Cl OH O–

Physical Properties of Ethers

1. Physical state: dimethyl ether and ethyl methyl ether are gases. All others are colourless liquids
with pleasant odours.
2. Dipolar nature: since ether molecule is bent (bond angle of 110°), the dipole moment of C–O bonds do
not cancel each other. As a result, ethers are slightly polar and have a net dipole moment.
3. Boiling point: ethers are isomeric with monohydric alcohol but their boiling points are much lower
than the isomeric alcohols because ethers cannot associate through hydrogen bonding. The boiling
point of ethers are close to the boiling points of alkanes.
4. Solubility: ethers are slightly soluble in water (but less than isomeric alcohol) due to the formation
of weak hydrogen bond between water and ether oxygen.
R δ– δ+
O H – O
δ+ δ– R
R
H O
R
5. Density: all ethers are lighter than water.

Do You Know?

Ethers are used as a solvent for Grignard reagent, since it can act as base towards acidic magnesium.
R'
R R
O : Mg :O
R R
Br

334 Organic Compounds Containing Oxygen – I

Chemical Properties of Ethers
Ethers are chemically less reactive as they do not have any active functional group. The ether linkage is
quite stable towards bases, oxidising agents, and reducing agents. However, under specific conditions,
ethers undergo the following reactions.
1. Reactions of ethereal oxygen: due to the presence of lone pairs on oxygen, ether behaves as Lewis
bases.
a. Action of concentrated acid: ethers behave as Lewis base and dissolves in cold concentrated
inorganic acids to form stable oxonium salts.
R R +
O : + HCl O – H Cl–
R R

b. Formation of coordination complexes: being Lewis bases, ethers form coordinate complexes,
known as etherates, with Lewis acid, such as BF3, AlCl3, FeCl3, R mgx.
R R
O : + BF3 O: BF3
R R

2. Reactions involving the cleavage of carbon-oxygen bond

a. Reaction with halogen acid: ethers are readily cleaved by concentrate HI or concentrated HBr.
373 K
R – O – R + HX R – OH + R – X
Alcohol
Al Alkyl halide
However, if excess of acid is used, the alcohol first formed reacts further with the halogen acid
to form the corresponding alkyl halide.
373 K
R – O – R + 2H
2HI 2R – I + H2O
373 K
+ 2HBr CH2 – CH2
+ H2O
O
CH2 CH2
THF
Br Br
Reactivity of HX is HI > HBr > HCl.
The oxygen of an ether is basic, like the oxygen of an alcohol. The initial reaction between an ether
and an acid is the formation of protonated ether. Cleavage then involves nucleophilic attack by hal-
ide ion on this protonated ether, with displacement of the weakly basic alcohol molecule.
H
.. SN1
R – O – R' + HX R — O — R' + – X R – X + R' OH
.. + Or
SN2 Weak base
good leaving
group
Such a reaction occurs much more readily than displacement of the strongly basic alkoxide ion
from the neutral ether.
–
R – O– R
R' + X R – X + R' O–

Strong base
se
poor leaving
aving
group

Organic Compounds Containing Oxygen – I 335

 Reaction of a protonated ether with halide ion like the corresponding reaction of a protonated
alcohol can proceed either by an SN1 mechanism or SN2 mechanism.
SN1 mechanism
H
sl
slow +
R – O – R' R + HOR'

SN1
R+ + X
– fast
RX
SN2 mechanism
H H H
– δ−
R – O – R' + X X R OR' R' SN2
R — X + HOR'
+ δ+

In case of unsymmetrical ethers, the site of cleavage depends on the nature of alkyl group, e.g.,
i. If one group is methyl and the other is 1° or 2° alkyl group, the reaction occurs by SN2
mechanism. Due to steric hindrance, the halide ion always attacks the smaller alkyl group,
i.e., CH3 group to give methyl iodide while the bulkier alkyl group gives the alcohol.
CH3 CH3
373 K
CH3 – CH – O – CH3 + HI CH3 – I + CH3 – CH – OH
S N2
If one group is methyl and other group is tert-alkyl group, the reaction occurs by SN1 mechanism
and the formation of products is controlled by the stability of the carbocation. Since tert-alkyl
carbocation is much more stable than methyl carbocation. Therefore, the alkyl halide is always
derived from tert-alkyl group and the alcohol from the smaller alkyl group.
CH3 CH3
373 K
CH3 – C – O – CH3 + HI CH3 – C – I + CH3 OH
S N1
CH3 CH3

Do You Know?

High polarity of the solvent present in concentrated HI favours SN1 mechanism. However, if cleavage
of tert, butyl methyl ether is carried out with anhydrous HI in ether, the low polarity of the solvent
(ether) would favour SN2 mechanism, and hence, I– ion will attack the less hindered methyl group
giving methyl iodide and tert-butyl alcohol.
CH3 CH3
Anhydrous HI/ether
her
CH3 – C – O – CH3 CH3I + CH3 – C – OH
SN2
CH3 CH3

In case of phenolic ethers, the cleavage occurs with formation of Phenol and alkyl halide. It
is probably due to the fact that phenyl oxygen bond has a partial double bond character due
to resonance. Therefore, its cleavage is relatively difficult as compared to alkyl oxygen bond.

336 Organic Compounds Containing Oxygen – I

 OH

O CH3 + CH3I

373 K I
+ HI

+ CH3OH

Diaryl ethers on the contrary are not cleaved by HI.

The reaction of HI with ethers forms the basis of Zeisel method for the estimation of alkoxy
groups, such as methoxy (–OCH3) and ethoxy (–OCH2 CH3) groups. The alkyl iodide (CH3I or
CH3CH2I produced as a result of action of HI) is absorbed in ethanolic silver nitrate solution
and silver iodide thus, formed is weighed.
ii. Reaction with sulphuric acid
1) With dilute H2SO4
Dil H2SO 4, ∆
R – O – R + H2O 2R OH
Under pres
pressu
sure
re
Alcohol
2) With concentrated H2SO4

R – O – R + Conc. H2SO4 R – OH + ROSO
SO3H

Alkyl hydrogen
hydroge
sulpha
sulp hate
ha
∆
CH3CH2 – O – CH2CH3 + Conc. H2SO 4 CH3CH2OH + CH3CH2 OSO 3H

Secondary and tertiary ethers however, form alkenes.

CH3 CH3
Conc. HSO
H2 4
CH3 – C – OCH3 CH3 – C = CH2 + CH3OH
∆
CH3
iii. Reaction with PCl5

R – O – R + PCl5 
 2RCl + POCl
3

iv. Reaction with acid chloride and acid anhydride

R – O – R + CH3COCl RCl + CH3COOR

R – O – R + (CH3CO)2 O 2CH3COOR

3. Reactions involving the alkyl group

a. Action of air and light: on exposure to air and light ethers are oxidised to hydroperoxide or peroxides.
OOH
light
ght
CH3CH2 – O – CH2CH3 + O2 CH3 – CH – OCH2CH3

1-Ethoxyethyl hydroperoxid
eroxide
eroxid

Organic Compounds Containing Oxygen – I 337

 It is a free radical reaction and oxidation occurs at the carbon atom next to ethereal oxygen to
form hydroperoxide.
These peroxides are very dangerous since they decompose violently at high temperature. Therefore,
serious explosion may occur during distillation of old samples of ether, if peroxides are not removed.
The presence of peroxides is indicated by formation of a red colour when the ether is shaken
with aqueous solution of ferrous ammonium sulphate and potassium thiocyanate; the peroxide
oxidises ferrous ion to ferric ion, which reacts with thiocyanate ion to give the characteristic
blood-red colour of the complex. Peroxides can be removed from ethers in a number of ways,
including warming with solutions of ferrous ion (which reduces peroxide) or distillation from
concentrated H2SO4 (which oxidises peroxides).
Ether peroxide formation is prevented by adding a little Cu2O to ether.
b. Halogenation
Cl Cl Cl
Cl2, dark
k Cl2, dark
k
CH3CH2 – O – CH2CH3 CH3CH2 – O – CH – CH3 CH3 – CH – O – CH – CH3
–HCl –HCl
hν
CH3CH2 – O – CH2 CH3 + 10 Cl2 CCll3CCll2 – O – CCll2 CCll3 + 10 HCl
(Excess)
s)

Ring Substitution in Aromatic Ethers

Aromatic ethers undergo electrophilic substitution in the ring at ortho and para positions.

O CH3 O CH3 O CH3

Conc. HNO3 + H2SO4 NO2

NO2

O CH3 O CH3 O CH3

Br
Br2 /CS2
+

Br
Aromatic ethers are relatively less reactive towards electrophilic ring substitution than the phenols.
Cleavage of Epoxides: due to the presence of highly strained three-membered ring, epoxides can undergo
acid-catalysed reactions with extreme ease, and unlike ordinary ether can be cleaved by base.
1. Acid catalysed cleavage: like other ethers, an epoxide is protonated by acid; the protonated epoxide
can then undergo attack by any of a number of nucleophilic reagents.
Z: Z

– C – C – + H+ – C – C – – C – C –

O O+ OH
Z: H

338 Organic Compounds Containing Oxygen – I

 Attack of water yields 1,2-diol.

– C – C – + H2O – C – C – + H+

O+ HO OH
H
1,2-diol
1,
Attack of alcohol gives a compound containing ether and alcohol.
H

– C – C – + R – O..: – C – C – + H+

O+ RO OH
H
Alkoxy alcoho
cohol
coho
Attack of halogen acid forms halohydrin.

– C – C – + HX – C – C – + H+

O+ X OH
H
Halohydrin
In case of unsymmetrical epoxides, the nucleophile attacks the more substituted carbon in acid
catalysed cleavage, i.e., attack occurs at the carbon that can best accommodate the positive charge
and the reaction on this carbon is SN1 like because bond breaking is faster than bond making in
the transition state.
CH3 CH3
.. δ +
CH3 O
.. H + CH3 – C – CH2 CH3 – C – CH2

O δ+
H O CH3OH

2. Base catalysed cleavage: unlike ordinary ethers, epoxides can be cleaved under alkaline conditions.
Here it is the epoxide itself, not the protonated epoxide, that undergoes nucleophilic attack.

z z
HZ
Z: + – C – C – – C – C – – C – C – + :Z

O O– OH

+
– + H
C2H5O N a + CH2 – CH2 CH2 – CH2 CH2 – CH2

O –
O OC2H5 OH OC2H5

NH3 + CH2 – CH2 CH2 – CH2

O OH NH2

If the epoxide is unsymmetrical, in base-catalysed ring opening, nucleophile attacks the less sub-
stituted carbon atom, it is due to the fact that it follows SN2 reaction.

Organic Compounds Containing Oxygen – I 339

 CH3 CH2OH
CH2CH2O– + CH2 – CH CH3 CH3CH2 O CH2 CH CH3

O OH
3. Cleavage by Grignard reagents

R – MgX
Mg + CH2 – CH2 R – CH2 CH2 O — MgX

O H+
R CH2CH2 OH
1° alcohol
It provides a path of preparation of 1° alcohol containing two more carbons than the Grignard
reagent.
+
H
CH3MgBr
Br + CH2 – CH2 CH3 CH2CH2OH

O
+
H
MgBr
Br + CH2 – CH2 CH2 CH2OH
O
2 – Phenylethano
anoll
ano

Practice Exercise

Multiple Choice Questions (Single Choice

Correct) 4. For the reaction:
ZnX2
1. Two moles of ethanol are burnt. The amount C H5 OH  HX   C2H5 X  H2 O , the
2
of CO2 obtained will be _____.
(A) 132 g (B) 44 g reactivity order for halogen acid is _____.
(C) 88 g (D) 176 g (A) HBr > HI > HCl
(B) HI > HCl > HBr
2. 3-methyl-2-butanol on treatment with HCl (C) HI > HBr > HCl
gives predominantly _____.
(D) HCl > HBr > HI
(A) 2-chloro-2-methylbutane
(B) 2-chloro-3-methylbutane PCl Alc . KOH ( i) Conc . H SO
5. Z 
5
 X 
  Y 
2 4
 Z.

(C) 2, 2-dimethylpentane ( 2 ) H2O; boil

Z is _____.
(D) None of the above
(A) CH3 — CH2 — CH2 — OH
3. Excess chlorine reacts with ethanol to give
(B) CH − CH − CH
_____. 3 3
(A) ethyl chloride |
OH
(B) chloroform
(C) acetaldehyde (C) (C2H5)3 C — OH
(D) chloral (D) CH3 — CH = CH2

340 Organic Compounds Containing Oxygen – I

6. The end product of the following sequence 12. The order of reactivity of the following
is _____. alcohols towards concentrated HCl is _____.
 B 
N a
KCN lc 
alc H O LiAlH
CH3Br 
(A) 
3
 4
 (C) CH3
ether CH3 CH3 CH3
F OH F
(A) CH3CHO (B) CH3CH2OH Ph OH
OH OH
(C) CH3COCH3 (D) CH4 (I) (II) (III) (IV)

7. Ethyl acetate is treated with excess of (A) I > II > III > IV (B) I > III > II > IV
C 2 H 5 MgBr and the reaction mixture is (C) IV > III > II > I (D) IV > III > I > II
hydrolysed with water. The product is _____.
13. An alcohol on oxidation is found to give
(A) C2H5OH (B) (C2H5)2CHOH
CH3COOH and CH3CH2COOH. The alcohol is
CH3 _____.
| (A) CH3CH2CH2OH
(C) CH3COOC2H5 (D) C2H5 − C − O
OH
| (B) (CH3)2 C(OH)CH2CH3
C2H5 (C) CH3(CH2)2CHOH
(D) CH3CH(OH) CH2CH2CH3
K2Cr
Cr2O7
8. C3H8 O 
HS
SO
O
 CHI3 .
 C3H6 O 
2 I N
NaOH
CH3 Cold CrO
2 4 Warm
14.  (A) 
3
(B) ,
alkaline KMnO4 AcOH
Starting compound is _____.
(A) CH3CH2CH2OH (A) and (B) are _____.

(B) CH − CH − CH CH3 CH3

3 3
| (A) OH OH
OH OH O
(C) CH3 – O – CH2 – CH3 CH3 CH3
(D) CH3–CH2 – CHO (B) OH OH
OH O
9. With anhydrous zinc chloride, ethylene glycol CH3 CH3
gives _____.
(C) OH O
(A) formaldehyde (B) acetylene
OH O
(C) acetaldehyde (D) acetone
(D) None of the above
OH
10. The IUPAC name of is _____.
15. Periodiate oxidation of 1, 2 cyclopentanediol
(A) 3-Methylcyclobut-1-en-2-ol gives _____.
O
(B) 4-Methyl cyclobut-2-en-1-o-1 O
(C) 2-Methylcyclobut-1-en-3-ol (A) (B)
(D) 1-Methyl cyclobut-2-en-4-ol O
O

11. An organic compound (A) reacts with CH3MgI to CHCH2CH2CH2CH

form an addition product, which on hydrolysis (C) (D)
O O O
forms the compound (B). Compound (B) gives
blue-coloured salt in Victor-Meyer’s test.
The compounds (A) and (B) respectively are
_____. 16. Glycerol on heating with potassium
(A) acetaldehyde, tert-butylalcohol bisulphate yields _____.
(B) acetaldehyde, ethylalcohol (A) acetone (B) acrolein
(C) acetaldehyde, isopropylalcohol (C) glyceraldehyde (D) propanol
(D) None of the above

Organic Compounds Containing Oxygen – I 341

 17. Which set of the following reagents (A to NaBH
22. CH3  CH  CH  CHO
 CHO 
4
X
D) would you select to convert C6H5COCH3,
What is X?
(acetophenone), to the following alcohol?
(A) CH3CH2CH2CH2OH
CH3 CH3
(B) CH3  CH  CH  CH2OH

C 6H5 — C — CH — CH3 (C) CH3CH2CH2CHO
OH (D) CH3CH2CH(OH)CH3
(A) CH3CH2CH2MgBr and acid hydrolysis
23. Ethylene glycol reacts with PI3 to yields _____.
(B) CH3CH(Br)CH3, AlCl3
(C) (CH3)2 CHMgBr and acid hydrolysis
(D) CH3CHOHCH3, Zn (A) (B)

18. The three products obtained in the reaction

(C) (D) None of the above
between glycerol and hydroiodic acid would
appear in the order _____.
(A) propene, allyl iodide, and isopropyl iodide
(B) allyl iodide, propene, and isopropyl iodide 24. CH2  CH2 



4
 X

( i) O
OsO
( ii) ethanolic Na
a2S2O3
(C) allyl iodide, isopropyl iodide, and propene
X is _____.
(D) isopropyl iodide, allyl iodide, and propene
(A) CH3CHO (B) CH2OHCH2OH
(C) CH2OHCH3 (D) CH3CH2SO2
19. In the reaction sequence
hypochlorus acid
CH2  CH2 
 A 
B
 25. Which of the following oxidising agent will
convert glycerol to mesoxalic acid?
CH2 OH (A) Dilute HNO3 (B) Concentrated HNO3
|
CH2 OH (C) Bi(NO3)3 (D) NaOBr

A and B are respectively ____________.

26. HOCH2 CH2 OH  COCl 2  pyridine


 
(A) CH2 — CH2 and heat
OH
O (A) Cl (B)
(B) CH3CH2Cl and NaOH OH
(C) CH3CH2OH and H2SO4 OCl
(D) CH2ClCH2OH and NaHCO3 (C) O (D)
OCl
20. The reaction of ethylene glycol with HIO4 27. Which of the following gives red colour in
gives _____. Victor-Meyer’s test?
(A) H2 C = CH2 (B) HCHO (A) Sec-Butyl alcohol (B) Isopropyl alcohol
(C) n-propyl alcohol (D) tert-Butyl alcohol
(C) CH3 −− CHO (D) HCOOH
28. By which of the following reactions, 2-Phenyl
21. Which of the following reagents can convert ethanol is obtained?
glycerol to acrolein? (A) HCHO + PhMgBr/H2O
(A) HIO4
(B) KHSO4 (B) CH3CHO
CHO + P
PhMgBr
PhMgB
hMgBrr/H2O
(C) HNO3 + H2SO4 (concentrated) (C) CH3OH + PhMgBr/H2O
(D) Anhyd. CaCl2
(D) + PhMgBr/H2O
CH2 CH2

342 Organic Compounds Containing Oxygen – I

29. Which of the following amongst is the 37. Phenol is heated with pjthalic anhydride
strongest acid? in presence of concentrated H2SO4. The
products gives pink colour with alkali. The
(A) HC ≡ CH (B) C6H6 product is _____.
(C) C2H6 (D) CH3 OH (A) phenolphthalein
(B) Bakelite
30. Phenol is less acidic than _____. (C) salicylic acid
(A) ethanol (B) o-nitro phenol
(D) None of the above
(C) methanol (D) p-methyl phenol

38. When phenol is reacted with chloroform and

HO CH CH — CH — COOH an alkali like NaOH, the compound formed
31.
is salicyaldehyde. If we use pyrene in place
of chloroform the product obtained is _____.
OH
(A) salicylaldehyde
will show _____.
(B) phenolphthalein
(A) geometrical isomerism
(C) salicyclic acid
(B) optical isomerism
(D) cyclohexanol
(C) geometrical and optical isomerism
(D) neither geometrical nor optical isomerism 39. In the following compound, the order of
acidity is _____.
32. Phenol reacts with bromine water in carbon
disulphide at low temperature to give _____. OH OH OH OH
(A) o-bromophenol
(B) o-and p-bromophenol
NO 2
(C) p-bromophenol CH3 NO 2
(D) 2,4,6-tribromophenol
(A) III > IV > I > II (B) I > IV > III > II
(C) II > I > III > IV (D) IV > III > I > II
33. A new carbon-carbon bond formation is
possible in _____.
(A) Reimer-Tiemann reaction 40. The reaction of aromatic acyl chloride and
phenol in the presence of a base NaOH or
(B) Friedel-Crafts alkylation
pyridine is called _____.
(C) Clemmensen reduction
(A) Kolbe reaction
(D) Both (A) and (B)
(B) Perkin reaction
(C) Sandmeyer reaction
34. Which compound is known as the oil of
(D) Schotten Baumann reaction
winter green?
(A) Phenyl benzoate (B) Phenyl salicylate
41. Which of the following reagent gives violet
(C) Phenyl acetate (D) Methyl salicylate
colour with phenol?
(A) Anhyd. AlCl3 (B) NaOH
35. For the reaction of phenol with CHCl3 in
presence of KOH, the electrophile is _____. (C) Neutral FeCl3 (D) Dilute HCl
(A) (B) CCl2
42. The product obtained by Kolbe’s reaction is
(C) CHCl2 (D) None of the above acetylated, then the final product formed is
_____.
36. Phenol and benzoic acid can be distinguished (A) salol
by _____.
(A) aqueous NaHCO3 (B) aqueous NaNO3 (B) oil of winter green

(C) aqueous NaOH (D) concentrated H2SO4 (C) aspirin

(D) salicyclic acid

Organic Compounds Containing Oxygen – I 343

 43. Which of the following compounds has the 48. When phenol is treated with CHCl3 and NaOH
highest acidity? followed by acidification, salicylaldehyde is
obtained. Which of the following species is
OH
OH OH
OH OH
OH involved as reaction
OH
OH intermediate?
O OH
(A) (B) H CH3
(A) (B)
NO
NO22
CH
CH33 NO
NO22 CCl2

OH
OH OH OH O O
OH OH
O O
(C) (D) CHCl2
H
NO22
NO (C) (D)
CH33
CH NO22
NO CCl2

44. When oxygen is passed through an ethereal OH

solution of phenyl magnesium bromide
followed by acidification, a compound is 49. In the following sequence, the product (C) is
obtained whose boiling point is 182°C. This _____.
compound is _____. Na CH3I
CH3CH2 OH (B) (C)
(A) bromobenzene (B) toluene
(C) 2-butanol (D) phenol (A) CH3 CH2OH (B) CH2 = CH2
45. Benzenediazonium chloride reacts with (C) CH3CH2CH2OH (D) CH3 CH2OCH3
phenol in a solution whose pH is in the range
of 9-10 at 0°-5° C. The product obtained is 50. The product formed in the following reaction
_____. C6H5 – O – CH3 + HI Heat eat is _____.
(A) phenolphthalein
(B) methyl orange (A) C6H5OH and CH3I (B) C6H5I and CH3OH
(C) benzene (C) C6H5CH3 and HOI (D) C6H6 and CH3 OI
(D) 4-hydroxyazobenzene
46. 51. Reaction of CH2 – CH2 with RMgX followed
O — CH2 — CH CH2 OH
CH2 — CH CH2
300°C
O
by hydrolysis produces _____.
(A) Fries rearrangement (A) RCHOH R
(B) Cope rearrangement (B) RCH2CH2OH
(C) Beckmann rearrangement (C) RCHOH CH3
(D) Claisen rearrangement (D) R CH = CHOH

47. A compound ‘X’ is treated with methanol 52. Which of the following cannot be made by
and few drops of concentrated H2SO4, a using Williamson’s synthesis?
compound ‘Y’ is obtained, which has winter (A) Methoxybenzene
green odour. X is _____. (B) Benzyl-p-nitrophenyl ether
OH
OH OCH
OCH33 (C) Tert-butyl methyl ether
OH
OH COOCH
COOCH33 OCH
OCH33COOH
COOH (D) Di-tert-butyl ether
(A) COOCH
COOCH33 (B) COOH
COOH
53. In the following reaction,
OH
OH OH
OH Red P + HI
OH
OH COOH OH
OH CH C2H5O C2H5 + 4HI 2X + HO,
H2 X
COOH CH33
COOH
COOH CH
CH33
is _____.
(C) (D)
(A) ethane (B) ethylene
(C) butane (D) ethylene

344 Organic Compounds Containing Oxygen – I

54. Tetrahydrofurane is treated with excess of (A) H2SO4 (B) KSCN
HBr at 373 K. The product is _____. (C) HgCl2 (D) NaCl
(A) 1, 4-dibromobutane
(B) 1-bromo-2-butene
62. C2H5OH 
A
 C2H5I 
B
 C2H5 -- O-- C2H5
(C) 4-bromo-1-butanol
Which of the following is the correct
(D) 4-bromo-1-butene sequence of reagent A and B?
(A) HI and C2H5OH
55. Sometimes explosion may occur while (B) PI3 and C2H5OH
distilling ether. It may be due to the
(C) P/I2 and C2H5ONa
presence of _____.
(A) oxides (B) peroxides (D) HI and C2H5ONa
(C) alcohols (D) chloroform
63. When an ether, O — CH2 is
56. The boiling points of this ethers are ___ than
those of ether. treated with HI. Possible product can be _____.
(A) lesser (B) equal
CH2I CH2OH I OH
(C) higher (D) None of the above
(A) I and IV (B) II and III
57. Purity of ether before using it as anaesthetic (C) I and II (D) III and IV
agent is tested by _____.
(A) KI + Starch (B) CuSO4
64. What is the final product of following
(C) H2SO4 (D) None of the above reaction?
+
58. Benzene diazonium chloride on reaction with H
phenol in weakly basic medium gives _____. OH
(A) diphenyl ether
(B) p-hydroxy azobenzene OH
(C) chlorobenzene (A)
OH
(D) benzene
OH
(B)
59. The reagents used for the preparation of
t-butyl methyl ether by Williamson’s method OH
will be _____. OH
(A) methoxide and t-butylbromide (C)
(B) methanol and 2-bromobutane OH OH
(C) 2-butanol
OH and methyl bromide
(D) tert-butoxide and methyl bromide (D)
OH OH
60. Tert-butyl methyl ether, on heating with HI,
gives a mixture of _____. OH
(A) tert-butyl alcohol and methyl iodide
(B) tert-butyl iodide and methanol –
65. OC 2H 5 A.
+ C2 H5 I
(C) isobutylene and methyl iodide Anhydrous
(D) isobutylene and methanol C2H 5OH
Identify A.
61. When aliphatic ethers come in contact with
air, they are slowly converted to peroxides. (A) C6H5 OC2H5 (B) C2H5 OC2H5
The presence of peroxide in ether can be
detected by adding ferrous ammonium (C) C6H5 OC6H5 (D) C6H5I
sulphate [Fe2+ ion] along with _____.

Organic Compounds Containing Oxygen – I 345

 66. Which one of the following will most readily 72. The increasing order of boiling points of the
be dehydrated in acidic condition? below mentioned alcohol is _____.
[2000] (I) 1, 2-dihydroxy benzene
(II) 1, 3-dihydroxy benzene
(A) (B) (III) 1, 4-dihydroxy benzene
(IV) hydroxy benzene
[2006]
(A) I < II < IV < III (B) I < II < III < IV
(C) IV < II < I < III (D) IV < I < II < III
(C) (D)

73. The reaction of

67. The compound that will react most readily CH OH with HBr gives
CH 3CH
with NaOH to form-methanol is _____.
[2001]
_____. [1998]

(A) CH3  4
NI (B) CH3OCH3
(C) (CH3)3S+I– (D) (CH3)3CCl
(A) CH3CHBrCH
CHBrCH2 OH
68. l-propanol and 2-propanol can be best
distinguished by _____. [2001]
(A) oxidation with alkaline KMnO4 followed
by reaction with Fehling solution (B) CH3CH 2CHBr OH
(B) oxidation with acidic dichromate followed
by reaction with Fehling solution
(C) oxidation by heating copper with acidic (C) CH3CHBrC
CHBrCH
CHBrCH
H2 Br
dichromate followed by reaction with
Fehling solution
(D) oxidation with concentrated H 2 SO 4 (D) CH3CH 2CHBr Br
followed by reaction with Fehling solution

OH

OC H
74. In the reaction the
69.  C2H5I  2 5
Anhydrous ( C H OH)
?
2 5
products are _____.
[2009]
[2003]
(A) C6H5OC2H5 (B) C2H5OC2H5 (A) Br OCH
H3 and H2
(C) C6H5OC6H5 (D) C6H5l
(B) Br and CH3 Br
70. The product of acid catalysed hydration of
2-phenylpropene is _____. [2004]
(A) 3-phenyl-2-propanol (C) Br and CH3OH
(B) 1-phenyl-2-propanol
(D) OH and CH3 Br
(C) 2-phenyl-2-propanol
(D) 2-phenyl-1-propanol 75. An unknown alcohol is treated with the ‘Lucas
reagent’ to determine whether the alcohol is
71. The best method to prepare cyclohexene from
primary, secondary, or tertiary. Which alcohol
cyclohexanol is by using _____. [2005]
reacts fastest and by what mechanism?
(A) concentrated HCl + ZnCl2 [JEE Main 2013]
(B) concentrated H3PO4 (A) Secondary alcohol by SN1
(B) Tertiary alcohol by SN1
(C) HBr
(C) Secondary alcohol by SN2
(D) concentrated HCl (D) tertiary alcohol by SN2

346 Organic Compounds Containing Oxygen – I

76. 2-chloro-2-methylpentane on reaction with Multiple Choice Questions (One or More
sodium methoxide in methanol yields_____. Choice Correct)
CH3
(A) C 2H 5CH 2C–OC
C–OCH
C–OCH
H3 (B) C2 H5CH 2C = CH2 78. Th e e t h e r O CH2

CH3 CH 3
when treated with HI produces _____.
[1998]
(C) C 2H 5CH = C – CH3 [JEE Main 2016]

CH 3 (A) CH2I CH2OH

(A) All of the above (B) (A) and (C)

(C) (C) only (D) (A) and (B)
CH2I (B) CHCH2I2OH CH2OH
I OH
77. The major product formed in the following
reaction is _____.
CH2I (C) CH2OH
I OH OH
I
O HI
Heat
at (D)
O I OH

[JEE Main 2018]

Comprehension Passage Based Questions

I Comprehension for Questions 79 to 81

(A)
Reimer-Tiemann reaction introduces an aldehyde
group, on to the aromatic ring of phenol, ortho
OH to the hydroxyl group. This reaction involves
electrophilic aromatic substitution. This is a
general method for the synthesis of substituted
salicylaldehydes as depicted below.
OH – 
(B)
OH ONa OH
CHO CHO
OH
aq. HCl
[l]
intermediate

CH3 CH3 CH3

(C) I (I) (II) (III)

I 79. Which of the following reagents is used in

the above reaction?
(A) aq. NaOH + CH3Cl
(B) aq. NaOH + CH2Cl2
(D) OH
(C) aq. NaOH + CHCl3
(D) aq. NaOH + CCl4.
I
80. The electrophile in this reaction is _____.
(A) :CHCl (B) +CHCl2
(C) :CCl2 (D) .CCl3.

Organic Compounds Containing Oxygen – I 347

 81. The structure of the intermediate I is _____. [2007]
–   –  – 
ONa ONa ONa
CH2Cl CCl3 CH2OH

(A) (B) (C) (D)

CH3 CH3 CH3

Match the Columns

82. Match each of the compounds in List I with its characteristic reaction(s) in List II. [2009]
List I List II
(A) CH3CH2CH2CN (P) Reduction with Pd – C/H2
(B) CH3CH2OCOCH3 (Q) Reduction with SnCl2/HCl
(C) CH3 – CH = CH – CH2OH (R) Development of foul smell on treatment with
chloroform and alcoholic KOH.
(D) CH3CH2CH2CH2NH2 (S) Reduction with diisobutylaluminium hydride
(DIBAL–H)
(T) Alkaline hydrolysis

Assertion and Reason Questions

Read the following statements and explanations, and answer as per the options given below.
(A) If both assertion and reason are correct, and reason is the correct explanation of the assertion.
(B) If both assertion and reason are correct, but reason is not the correct explanation of the
assertion.
(C) If assertion is correct but reason is incorrect.
(D) If assertion is incorrect but reason is correct.

83. Assertion: solubility of n-alcohols in water decreases with increase in molecular weight.
Reason: the relative proportion of the hydrocarbon part in alcohols increases with increasing
molecular weight, which permits enhanced hydrogen bonding with water.
[1988]
Subjective Questions

84. Give the IUPAC name of the following cyclic compounds.

H OH
CH2OH H OH

a. b. c. CH 3 H d.
H OH
CH3 CH3

85. Write the structures and names of the cyclic isomer of C4H7OH. Also indicate the chirality
(if any).

86. C 7 H 14 (A) decolourises Br 2 in CCl 4 and 87. Cyclobutyl bromide on treatment with
reacts with Hg(OAc)2 in THF-H2O followed magnesium in dry ether forms an organometallic
by reduction with NaBH 4 to produce a compound (A). The organometallic compound
resolvable compound (B) (i.e., a mixture of reacts with ethanal to give an alcohol (B)
d and l-optically active isomers, a racemic after mild acidification. Prolonged treatment
mixture). (A) undergoes reductive ozonolysis of alcohol (B) with an equivalent amount of
to form the same compound (C) (one of the HBr gives 1-bromo-1-methylcyclopentane (C).
mixture) obtained by oxidation of 3-hexanol Write the structure of (A), (B) and explain how
with KMnO4. Identify (A), (B), and (C). (C) is obtained from (B).

348 Organic Compounds Containing Oxygen – I

88. 0.037 g of alcohol, ROH was added to CH3MgI 94. (i) BH3 . THF KMnO4
B(C7H1 6O) C(C7H1 4O 2)
and the gas evolved measured 11.2 mL at A (C7H1 4)
(ii) H2O2/OH–
STP. What is molecular mass of ROH? On
dehydration, ROH gives an alkene, which O3/H2O/Zn

on ozonolysis gives acetone as one of the D

KMnO4 CH3CH – CHCH2 CH3
products. ROH on oxidation easily gives an
CH3 OH
acid containing the same number of carbon
atoms. Give structures of ROH and the acid
with proper reasoning. B and C both have chiral carbons. Identify
89. 0.369 g of a bromo derivative of a hydrocarbon A, B, C, and D.
(A) when vaporised occupied 67.2 mL at NTP.
(A) on reaction with aqueous NaOH gives (B). 95. Identify A to F in the following reaction.
(B) when passed over alumina at 250°C gives a O OH
neutral compound (C) while at 350° C it gives a. H+
a hydrocarbon (D). (D) when heated with HBr A
gives an isomer of (A). When (D) is treated
with concentrated H2SO4 and the product is ZnCl 2
diluted with water and distilled, (E) is obtained. CH2 CH CH3 + HBr B + C
b.
Identify (A) to (E) and explain the reactions.
OH
90. Compound (x) (C 5 H 8 O) does not react
appreciably with Lucas reagent at room MnO2
c. OH D
temperature but gives a precipitate with
ammonical silver nitrate. With excess of
Cl
MeMgBr, 0.42 g of (x) gives 224 mL CH4 at
STP. Treatment of (x) with H2 in presence of d. Hg(OAC)2 /H2O NaOH
E F
Pt catalyst followed by boiling with excess
NaBH4
HI gives n-pentane. Suggest the structure
of (x) and write the equations involved.
i. Hg(OCOCH3 )2
91. Compound (A) gives Lucas test in 5 minutes. 96. Br2 Zn THF – H3 O
A B C
When 6.0 g of (A) is treated with sodium metal CH2Cl2 CH3COOH (C 6H 10) ii. NaBH /OH –
4

1120 mL of hydrogen is evolved at STP.

Assuming (A) to contain one atom of oxygen What are A, B, and C in the above scheme
per molecule, write the structural formula of reaction?
of (A). Compound (A) when treated with PBr3
gives compound (B), which when treated 97. 0.022 g of an alcohol was added to CH3MgI
with benzene in presence of aluminium and the gas evolved measured 5.6 cm 3
chloride gives compound (C). Write the at STP. What is the molecular weight of
structure of B and C. alcohol? On dehydration, the alcohol
gives an alkene, which on ozonolysis gives
92. Compound (A), C10H12O gives off hydrogen 2-butanone as one of the products. Alcohol
on treatment with sodium metal and also on oxidation easily gives an acid containing
decolourises Br2 in CCI4 to give (B), C10H12OBr2. the same number of carbon atoms. Give the
(A) on treatment with I 2 in NaOH gives structure of alcohol and acid.
iodoform and an acid (C) after acidification.
Give structures of (A) to (C) and also of the 98. Complete the following sequence of
geometrical and optical isomers of (A). reaction.
O
93. Alcohol A (C10H18O) is converted to mixture of a. PBr3 Y CH2 — CH2
CH3CH 2OH X CH 3CH 2MgBr Z
alkenes B and C on being heated with KHSO4. H2O/H
+

Catalytic hydrogenation of B and C yields the

same product. Assuming that dehydration of CH3
–
dil. KMnO4 HIO4 OH
alcohol ‘A’ proceeds without rearrangement. b. X Y Z
Deduce the structure of alcohol A and alkene
CH3
B and C. Alkene B by ozonolysis forms
cyclopentanone.

Organic Compounds Containing Oxygen – I 349

 99. Show the steps involved in the hydration of 107. Complete the following equation and
cyclobutyl ethene in presence of concentrated comment.
H2SO4. Also give the products obtained. Me
KMnO4 CrO3
Me
? OH
100. Identify A, B, C, D, and E in the following AcOH
sequence of reaction. O
1 mol of H2 HBr
HC CH A B 108. Explain why hydration of 3-phenyl-1-butene
NaNH2
in dilute H2SO4 does not give 3-phenyl-2-
butanol, but instead 2-phenyl-2-butanol is
B i. 1 mol of H2
C D – E obtained.
ii. BH3/H2 O2, OH
109. An organic compound (A) has 76.6% C and
101. Give the mechanism of the given reaction. 6.38% H. Its vapour density is 47. It gives
characteristic colour with aqueous FeCI3
CH 3 3
CCH2 OH 
conc. HCl
  CH3 2 CClCH2 CH3 solution. (A) when treated with CO2 and
NaOH at 140oC under pressure gives (B),
102. Give the pinacol rearrangement mechanism which on acidification gives (C). (C) reacts
of the glycol, Ph2C(OH)C(OH)MePh. with acetyl chloride to give (D), which is a
well known pain killer. Identify (A). (B), (C)
103. An alcohol whose formula is C6H5CH2C(CH3)2OH and, (D) and explain the reactions involved.
is produced by the action of Grignard reagent. 110. An organic aromatic compound (A) on
It is found that the two different Grignard treatment with CHCl3 and KOH gives (B)
reagents G1 and G2 produce this alcohol on and (C), both of which, in turn, give the
reaction with K1 and K2, respectively. Give same compound (D) when distilled with Zn-
the structure of G1, G2, K1, and K2. dust. Oxidation of (D) yields (E) of formula
C7H6O2. The sodium salt of (E) on heating
104. A compound, H contains only carbon and
with sodalime gives (F) which can also
hydrogen. 1 mole of H reacts with 1 mole
be obtained by distilling (A) with Zn-dust.
of bromine to give a dibromo compound ‘I’
Identify (A), (B), (C), (D), (E) and (F).
(C5H10Br2). H on treatment with cold alkaline
KMnO4 forms a compound ‘J’ (C5H12O6). H
111. A compound (P) whose molecular formula
on ozonolysis gives equimolar quantities
is C7H8O gives a characteristic colour with
of acetone and acetaldehyde. Deduce the
neutral ferric chloride. (P) is insoluble in
structure of H, I, and J.
aqueous NaHCO3 but soluble in aqueous
105. Compound (X) gives positive Lucas test as NaOH. When P is reacted with bromine
soon as Lucas reagent is added. When 7.4 g water, it gives a compound (Q), whose
of (X) is treated with Na metal 1120 mL of molecular formula is C7H5OBr3. Give the
hydrogen gas is evolved at NTP. Assuming structural formula of (P) and (Q).
(X) contains one oxygen atom per molecule,
write the structure of (X). Compound (X) 112. Identify A to D in the following.
when treated with Na gives sodium salt, O
which when treated with bromo ethane gives
a. + 2HI A
(Y). Write the structure of (Y).

106. The analysis of a compound ‘O’ shows

that it contains 68.2% C and 13.6% of H.
Its molecular formula is 88. When this
+ HI B
b.
compound is treated with HCl and ZnCl2, O
turbidity appears immediately. When this
compound (O) is passed over Al2O3 at 350°C
it gives compound (P). (P) on ozonolysis c.
followed by hydrolysis gave two neutral
compounds (Q) and (R). Both (Q) and (R) gives
yellowish-red ppt with 2, 4-DNP reagent. But + HI D
(Q) gives positive Tollens’ test but (R) does d.
not. Identify (O), (P), (Q), and (R). O

350 Organic Compounds Containing Oxygen – I

113. An organic compound containing C, H, and Br
O exists in two isomeric forms (A) and (B).
0.108 g of an isomer gives 0.308 g of CO2 H Ph Nal, acetone
and 0.072 g of H2O. (A) is insoluble in NaOH
and NaHCO3 while (B) is soluble in NaOH. MeO H
(A) reacts with concentrated HI to give (C)
and (D). (C) can be separated from (D) by Ph
ethanolic AgNO3 solution and (D) is soluble in [1996]
NaOH. (B) reacts readily with bromine water
to give compound (E) of molecular formula c. (CH3 )2 CHOCH3 
HI ( excess ), heat
 2 Pr oducts
C7H5OBr3. Identify (A) to E. [1998]

AlCl
Cl3 NBS alc. KOH 118. An alcohol A when heated with concentrated
PhH + CH3 CH2 Cl P Q R H2SO4 gives an alkene B. When B is bubbled
aq. KOH through bromine water and the product
obtained is dehydrohalogenated with excess
114. S of sodamide, a new compound C is obtained.
(i) Hg(OCOCF
F 3 )2
S+R T The compound C gives D when treated with
(ii) NaBH
BH4 warm dilute H2SO4 in presence of HgSO4. D
can also be obtained either by oxidising A
Identify P, Q, R, S, and T in the above with KMnO4 or from acetic acid through its
sequence of reaction. calcium salt. Identify A, B, C, and D.
[1983]
115. An organic liquid (A), containing C, H, and
O with boiling point 78°C and possessing 119. Complete the following with appropriate
a rather pleasant odour, on heating with structures.
concentrated sulphuric acid gives a gaseous OH OH
product (B) with the empirical formula, CH2,
B decolourises bromine water, as well as, CHO
a.
alkaline KMnO4 solution and takes up one
mole of H2 (per mole of B) in the presence
of finely divided nickel at high temperature.
Identify the substances A and B. [1986]
[1979] b. SO 3H
fuming 1. NaOH(fuse)
H2SO 4 2.H
+

116. A compound (X) containing C, H, and O is [1992]

unreactive towards sodium. It does not add
bromine. It also does not react with Schiff ’s 120. An organic compound (A) on treatment with
reagent. On refluxing with an excess of acetic acid in the presence of sulphuric acid
hydroiodic acid, (X) yields only one organic produces ester (B), (A) on mild oxidation
product (Y). On hydrolysis, (Y) yields a new gives (C), (C) with 50% potassium hydroxide
compound (Z), which can be converted into followed by acidification with dilute
(Y) by reaction with red phosphorous and hydrochloric acid generates (A) and (D), (D)
iodine. The compound (Z) on oxidation with with phosphorus pentachloride followed
potassium permanganate gives a carboxylic by reaction with ammonia gives (E), (E) on
acid. Equivalent weight of this acid is 60. dehydration produces hydrocyanic acid.
What are the compounds (X), (Y), and (Z)? Identify the compounds A, B, C, D, and E.
Write chemical equations leading to the [1987]
conversion of (X) to (Y). [1981]
121. Complete the following reaction.
117. Write the structural formula of the main SO 3H OH
organic product formed when: [1985]

I ? CHCl3/NaOH
a. Ethanol 
2
NaOH
 ?

b. Predict the structure of the product in

the following reaction. [1988]

Organic Compounds Containing Oxygen – I 351

 122. An organic compound containing C, H, and 125. A compound D(C8H10O) upon treatment with
O exists in two isomeric forms A and B. An alkaline solution of iodine gives a yellow
amount of 0.108 g of one of the isomers gives precipitate. The filtrate on acidification gives
on combustion 0.308 g of CO2 and 0.072 g a white solid E(C7H6O2). Write the structures
of H2O. A is insoluble in NaOH and NaHCO3 of D, E and explain the formation of E.
while B is soluble in NaOH. A reacts with [1996]
concentrated HI to give compounds C and D.
C can be separated from D by the ethanolic 126. An optically active alcohol A(C6H10O) absorbs
AgNO3 solution and D is soluble in NaOH. B two moles of hydrogen per mole of A upon
reacts readily with bromine water to give catalytic hydrogenation and gives a product
compound E of molecular formula, C7H5OBr3. B. The compound B is resistant to oxidation
Identify, A, B, C, D, and E with justification by CrO3 an does not show any optical activity.
and give their structures. Deduce the structure of A and B.
[1991] [1996]

127. Identify X, Y, and Z in the following synthetic

123. Compound X (molecular formula, C5H8O) does scheme and write their structures.
not react appreciably with Lucas reagent at CH 3CH 2C C H
room temperature but gives a precipitate
( i ) NaNH H /PdB
BaSO
BaS
aSO
O
with ammonical silver nitrate. With excess  2
CH CH Br
 X 
2 4

3 2
of MeMgBr, 0.42 g of X gives 224 mL of CH4 alkaline KMnO
at STP. Treatment of X with H2 in presence Y  

4
Z
of Pt catalyst followed by boiling with excess Is the compound Z optically active? Justify
HI, gives n-pentane. Suggest structure of X your answer. [2002]
and write the equation involved.
[1992] 128. Identify (X) and (Y) in the following reaction
sequence.
O
124. Identify C(C4H8), which when treated with
H2O/H2SO4 gives C4H10O, which cannot be H3C C CH3
OH
resolved into optical isomers. O3 NaOH(a(aq)
H
+

[1993] (X) (Y) q)

∆ Zn – CH
H3 C
COOH

[2005]

Answer Key

Multiple Choice Questions (Single Choice Correct)

1. (D) 2. (A) 3. (D) 4. (C) 5. (B) 6. (B) 7. (D) 8. (B) 9. (C) 10. (B)
11. (C) 12. (C) 13. (D) 14. (A) 15. (D) 16. (B) 17. (C) 18. (B) 19. (D) 20. (B)
21. (B) 22. (B) 23. (C) 24. (B) 25. (C) 26. (C) 27. (C) 28. (D) 29. (D) 30. (B)
31. (C) 32. (B) 33. (D) 34. (D) 35. (B) 36. (A) 37. (A) 38. (C) 39. (D) 40. (D)
41. (C) 42. (C) 43. (C) 44. (D) 45. (D) 46. (D) 47. (A) 48. (A) 49. (D) 50. (A)
51. (B) 52. (D) 53. (A) 54. (A) 55. (B) 56. (C) 57. (A) 58. (B) 59. (D) 60. (B)
61. (B) 62. (C) 63. (A) 64. (C) 65. (B) 66. (C) 67. (C) 68. (C) 69. (A) 70. (C)
71. (B) 72. (C) 73. (B) 74. (D) 75. (B) 76. (A) 77. (A)

Multiple Choice Questions (One or More Choice Correct)

78. (A) and (D)

Comprehension Passage Based Questions

79. (C) 80. (C) 81. (B)

352 Organic Compounds Containing Oxygen – I

Match the Columns

82. (A→ P,Q,S), (B→ S,T), (C→ P), (D→ R)

Assertion and Reason Questions

83. (C)

Subjective Questions

84. a. 1-cyclopentenyl methanol b. 3-cyclohexen-1-ol

c. trans-2-methylcyclopentanol d. 4, 4-dimethyl-2-cyclohexen-1-ol

CH2OH CH 3
85. a. OH b. c.
H OH
H

H OH
CH 3 OH * *
d. * * e. CH 3 H
H H

OH
|
86. (A) CH3 CH2 CH2 C − C
CHH2 CH
CH3 (B) CH3 CH2 CH2 C * −CCH
H2 CH
CH3 (C) CH3CH2CH2 − C − C
CH H2CH
CH3
|| | ||
CH2 CH3 (B) O

OH
MgBr C — CH3
87. , 88. CH2 CH2 CH2 C  CH
CH  2C
CHH3MgB
MgBr
gBr  2C
CHH4
(A) H | ( x)
(B)
OH
CH CHCOOH
CHCOOH
CH CH C CH3
89.
ONa
(A) (C)

90.
OH (B) (C)
(A)

O OH O
CH CH2 CH3
91. H+ CH2 CH CH3
Br Br
(A) (B) (C)

Cl
O

(D) O
OH
(E) (F)
92. *

Organic Compounds Containing Oxygen – I 353

 Br OH
93.
Br
(A) (B) Cyclohexano
(C)

CH 3 CH3

94. CH3 — CH 2 C — CH 2 CH 3 — CH2 CH COOH

2-Methyl butanoic acid
H OH
2-Methyl butanol

95. a. CH 3CH 2Br ; Mg/ethe , CH 3 — CH2 — CH2 — CH2 — OH

(X) (Y) (Z)
CH3 CH3
OH
OH O
b. O CH 3
OH
CH3 CH3
(X) (Y) O
(Z))
(Z

96. Cis and trans-2-methyl

-2-methyl cyclopentanol

–
97. H2C CH 2 H3C CH 2Br HC C HC C — CH2 CH3 HOCH2CH2CH2CH3
(A) (B) (C) (D) (E)

98. * 99. *
O
CH3
100. CH2MgBr C O CH3MgBr CH2 — C CH3
CH3
GI KI G2 K2

CH 3 CH3 CH3

101. CH3 — C CH — CH 3 CH3 — C CH — CH3 CH3 — C CH — CH3

(H)
Br Br OH OH
2,3-Dibromo, 2-methyl butane 2-Methyl butan-2,3-diol
(I) (J)

CH3 CH3

102. CH 3 C — OH CH3 C — OCH

H 2CH
CH 3

CH3 CH3
tert-butanol tert-Butyl ethyl ether
(Y)
(X)

CH3
CH 3 CH3

103. CH 3 — CH2 C — OH CH 3CH C — CH 3 CH 3CHO O C — CH3

2-Methyl but-2-ene (Q) (R)
CH3 (P)

(O))
(O

354 Organic Compounds Containing Oxygen – I

104. *
105. *

OH OH OH OOCCH3
106.
COONa COOH COOH
(A) (B) (C)
(D)
Phenol Sod.salicylate
e salicylic acid
id
Pain killerr
(Aspirin)
OH OH OH
CHO H CHO

107.

(A) (B) (D) (E) (F)

CHO
(C)
OH OCH 3 OH OH OH
COONa COOH COOCH 3

108. + NaI

(A1) Anisole Sodium salicylate Salicyclic acid Methyl salicylate

(A2) (A3) (A4)
(A4) (A5)
(A5)

109. *
110. *
OH OH
Br Br
111.
CH3 CH 3
(P) Br
(Q)
I
I I I
HO
112. a. b. c. d. OH
OH I
OH OH OH

Br Br
CH3I
113. (C)
CH3
(A) (B) (D)
Br
(E)

OH
CH2CH 3 CHBrCH3 CH = CH2 CH CH3 CH3 CH OCH

114. CH3

(P) (Q) (R) (S) (T)

115. C H OH , C2H4
2 5
116. C2H 5OC 2H5, 2C2H5II, 2C
C2H5O
OH
ethyl alcohol ( A ) (B) X Y Z

Organic Compounds Containing Oxygen – I 355

 I

Ph H H3C
117. a. CH3CHO b. MeO H c. CH(OH) + CH3 I
H3C
Ph

OH
118. CH3 CH CH3 , CH3CH CH2,CH3CH CH,CH 3COCH 3
A B C D

OH

119. a. CHCl3/KOH, 60°C 3-5 atm b.

OH

OH A – CH3OH (Alcohol, Methanol)

B – CH3COOC
COOCH
COOCH H 3 (Ester, Methyl acetate)
120. C – HCHO (Aldehyde, Formaldehyde)
D – HCOO
OOHH (Acid, Fo
Form
rmic
ic ac
acid
id))
OH E – HCON
ONHH2 (Amide, Formamide).

OH
CHO
121. Fuse with NaOH;

OCH 3 OH OH OH
Br Br
,
122. , CH3I, ,
C
CH 3 CH3
(Anisole) (m-cresol)
Br
(C7H5O
OBr3)

123. HC C CH 2CH 2 CH 2OH 124. trans-2-butene

CH3 CH 3

125. CH CH 3 , COOH 126. HC C C OH,CH3CH 2 C OH

D OH E
CH2CH 3 CH 2CH 3
A B

CH2CH 3 O
CH3 CH3
HO H
127. 128. , C
HO H C H
(X)
CH2CH 3 O
Z (Y)

356 Organic Compounds Containing Oxygen – I

 Solutions

Multiple Choice Questions (Single Choice 8. (B)

Correct) O
K2Cr2O7
CH 3 — CH — CH3 CH3 — CH — CH3
1. (D) H2SO 4
2C2H5 OH  6O2 
 4CO2  6H2 O OH

Amount of CO2 obtained = 4 × 44 = 176 g I2 + NaOH

CHI3 + CH3 COONa
2. (A)
CH3 9. (C)
+ CH2OH Anhydrous ZnCl CH2
—

CH3 — CH — CH — CH3 H CH3 — CH — CH — CH3 2

OH + OH (– H2O)
2 CH2OH CHOH
CH3
Vinyl alcohol
CH3
(unstable)
–H2O 1,2 hydride
CH3 — C — CH — CH3 CH3 — C — CH2 — CH3
+ shift +
H
CH3
Tautomerises
2° carbocation 3° carbocation CHO
(less stable) (more stable)
CH3 10. (B)
Cl–
CH3 — C — CH2 — CH3 2 1
OH
Cl

3. (D)
2 Cl 2 Cl 3 4
CH3 CH2OH  CH3CHO  CCl 3CHO 4-Methylcyclobut-2-en-1-ol
4. (C) 11. (C)
Large is bond length of H – X, easier is its
( i) CH3MgI
dissociation.
CH3 CHO   CH3 − CH − CH3
5. (B) ( ii) H /H2O
(A)
|
PCl5
CH3 — CH — CH3 CH3 — CH — CH3 OH
(B )
—

(X)
OH Cl
(Z) Victor- Meyer ' s
alc. KOH H2O
 Blue colouration
test
CH3 — CH = CH2 CH3 — CH — CH3
—

(Y) OH 12. (C)

(Z) The order of reactivity depends upon the
6. (B) stability of carbocation formed.
+ + +
KCN  alc  H O
CH3Br 
 CH3 CN 
3
 CH3 COOH i.e., FCH2 C HCH3 , FCH2 CH2 C HCH3 , CH3 C HCH3
Li AlH +

4
 CH3 CH2 OH and Ph C H2. Since the relative stabilities of
ether
these carbocations follow the order.
7. (D)
C 2H5   
Ph C H2  CH3 C HCH3  FCH2 CH2 C HCH3
CH3 — C — OC 2H5 + C 2H5MgBr CH3 — C — OC 2H5

O OMgBr
 FCH2 C HCH3
C 2H5 C 2H5
∴ The order of reactivity of the alcohols
(i) C 2H5 MgBr
CH3 — C — OH CH3 — C = O (I, II, III, and IV) follows the sequence IV >
+
(ii) H3O III > II > I.
C 2H5

Organic Compounds Containing Oxygen – I 357

 13. (D) 18. (B)
CH3 — CH — CH2 — CH2 — CH3 CH2OH CH2I CH2
+3 HI –I2
OH [O] CHOH CHI CH
–3 H2O
O CH2OH CH2I CH2I
CH3 — C — CH2 — CH2 — CH3 glycerol (unstable) Allyl iodide
[O]
CH3 CH3 CH3
CH3COOH + CH3CH2COOH HI – I2 HI
CHI CH CHI
14. (A)
CH2I CH2 CH3
CH3 CH3
Cold unstable Propene Isopropyl iodide
OH
alkaline KMnO 4
OH 19. (D)
(A) CH2 CH2Cl CH2OH
CH3 HOCl aq NaHCO 3
CrO 3
OH CH2 CH2OH CH2OH
AcOH
O
20. (B)
(B) C H2OH
+ HIO4 2HCHO + H2O + HIO3
15. (D) C H2OH
O 21. (B)
HIO 4
CH 2OH CH 2 CH2
OH KHSO 4 Heat
OH CHOH C CH
–2H2O
O CH 2OH CHOH CHO
16. (B) Acrolein

CH2 OH CH2 CH2 22. (B)

NaBH
CHOH
KHSO4
C Tautomerires CH CH3  CH  CH  CHO 
4

–2 H2O Crotonaldehyde
CH2OH CHOH CHO CH3  CH  CH  CH2OH
unstable Crotonyl alcohol
Acrolin
NaBH4 reduces –CHO group and not double
17. (C)
bond.
O OMgBr CH3
23. (C)
C — CH3 H3C — C — CH — CH3 CH 2OH PI 3 CH2

CH 2OH CH2
(CH3)2 CH Mg Br

24. (B)
+ CH2 O O CH2 — O O ethanolic Na SO CH2OH
H3O 2 3
+ Os Os
CH2 CH2 — O O CH2OH
O O
Ethylene glycol
OH CH3
25. (C)
CH3 — C — CH — CH3 Glycerol will give different products with
different oxidising agent.
Dilute HNO3 gives a mixture of glyceric acid
and tartronic acid.
Concentrated HNO3 gives glyceric acid.
Bi(NO3)3 gives meso-oxalic acid.
NaOBr gives glyceraldehyde and
dihydroxyacetone.

358 Organic Compounds Containing Oxygen – I

26. (C) 34. (D)
OH Cl Oil of winter green is methyl salicylate.
Pyridine
+ O O OH
–2HCl
COOCH3
OH Cl

27. (C)
In Victor-Meyer’s test, primary alcohols give
35. (B)
red colour, secondary alcohols give blue
Electrophile in Reimer-Tiemann reaction
colour, and tertiary alcohols give no colour.
is dichlorocarbene (: CCl2). For detailed
28. (D) mechanism refer to the theory.
Ph OMgBr
H2O
Ph OH
36. (A)
+ PhMgBr
Phenol being weak acid does not react with
NaHCO3.
CH 2 — CH2 OH
37. (A)
C C
Conc. H2SO4
O O
– H2O
29. (C) C C
Order of acidity is given below.
O
CH3 OH  CH  CH  C6H6  C2H6 H H

30. (B) OH OH
o-nitrophenol is more acidic than phenol due
Phenolphthalein
to presence of electron withdrawing group
(–NO2). OH OH

31. (C) 38. (C)

H OH OH
HO COOH
CH CH — C — COOH
+ CCl4 + NaOH
OH
Due to the presence of different substituents 39. (D)
around double bond, it will show geometrical Electron withdrawing group like NO2 disperses
isomerism. negative charge on phenoxide ion, thus,
The compound also contains a chiral carbon increasing the acidic character of phenol. The
due to which it will show optical isomerism effect is more pronounced at p-position than
also. at m-position. Electron releasing group like CH3
32. (B) intensifies the negative charge on phenoxide
OH OH OH ion and thus, makes phenol less acidic.
Br2 /CS2 Br 40. (D)
+ C6H5COCl  C6H5OH 
NaOH

273 K or Py

Br C6H5COOC6H5  H2O
33. (D) 41. (C)
CH3 Phenol gives violet colour with neutral FeCl3.
anhy AlCl 3 42. (C)
+ CH3Cl The product obtained by Kolbe’s reaction

Friedel - Crafts reaction

Friedel - Crafts reaction
is salicyclic acid . When it is

OH OH OH
CHO
+ CHCl3 + KOH + acetylated, it gives (Aspirin or
CHO
(Reimer - Tiemann reaction) acetylsalicyclic acid).

Organic Compounds Containing Oxygen – I 359

 43. (C)
The presence of electron withdrawing group (–NO2) at ortho or para position increases the acidity
of phenol and presence of electron donating group (–CH3) makes phenol less acidic.
44. (C)
MgBr OMgBr OH

+
1 Dry H /H2 O
+ O + Mg(OH)Br
2 2 ether
Phenol
(Boiling point = 182°C)
45. (D)
+ – –HCl +
N NCl + OH N N OH
0°-5° C
pH 9-10 4-Hydroxyazobenzene
(weakly alkaline)

46. (D)
In Claisen rearrangement, allyl group migrates from phenolic oxygen to the ortho position of benzene
ring.
47. (A)
OH OH
COOH COOCH 3
conc. H2 SO4
+ CH3 OH

Salicylic acid Methyl salicylate

(X) (Oil of winter green)

48. (A)
A1 gives violet colour with neutral FeCl3, thus, it must be phenol. Phenol is soluble in NaOH.
– +
OH O Na OCH 3

CH3I
+ NaOH + H2 O + NaI

(A1) Anisole
(A2)

A2 does give violet colour as it does not have = C — OH group.

–
O Na OH OH
COONa COOH
400 K dil. HCl
+ CO2
4 atm.

Sodium salt Sodium salicylate Salicyclic acid

of A1 (A3) (A4)

A4 gives violet colour with neutral FeCl3 due to the presence of  C  OH group.
–
O Na OH
COOH COOCH 3
conc. H2SO4
+ CH3OH + H2O

A4 Methyl salicylate
(A5)

Methyl salicylate is used as medicine for strains and aches.

49. (D) 51. (B)

Na CH3I CH2 – CH2 + R MgX R CH2CH 2OMgX
CH3 CH2 OH CH3 CH2 ONa CH3CH2 O CH3

50. (A) O H2O

C6H5 – O – CH3 + HI 
 C6H5OH + CH3I
R CH2CH2OH

360 Organic Compounds Containing Oxygen – I

52. (D) 57. (A)
To prepare di-tert-butyl ether by Williamson’s Impure ether, i.e., ether which contains
synthesis, we need tert-butyl bromide and peroxide will liberate I2 from KI which will
sodium tert-butoxide. Since tert-butyl give blue colour with starch.
bromide, being a 3° alkyl halide, prefers to
58. (B)
undergo elimination rather than substitution,
the product obtained is isobutylene rather + –
N2Cl + OH
than di-tert-butyl ether.
CH3 CH3

+ – – NaBr (ii) H+
CH3 – C – Br + Na O – C – CH (i) NaOH
3

CH3 CH3
N N— OH
CH3 CH3
59. (D)
CH3 – C = CH2 + CH3 – C – OH Tertiary halides do not undergo Williamson’s
synthesis. So reagents used are t-butoxide
CH3 and methyl bromide.
53. (A) CH3 CH3
HI Red P + HI
C 2H5OC2H5 2C2H5I 2C2H6
(cleavage) CH3 – C – ONa + CH3I CH3 – C – O – CH3
Reduction
54. (A)
CH3 CH3
373x
+ 2HBr
Br Br 60. (B)
O
CH3 CH3
55. (B)
Ether peroxide present in ether explodes 373 K
violently during distillation of ether. CH3 – C – O – CH3 + HI CH3 – C – I + CH3OH
SN1
56. (C)
Molecular weight of thioethers are more than CH3 CH3
ethers.
61. (B)
The presence of peroxide is indicated by the formation of red colour on adding Fe2+ and KSCN.

 Fe  SCN 
 2
Peroxide  Fe2  Fe3 
SCN

Red in colour

62. (C)
P /I C H ONa
C2H5 OH 
2
 C2H5I  2 5
  C2H5 OC2H5
( Williamson ' s synthesis)

63. (A)
HI
O — CH2 OH + ICH2

64. (C)
+
+ +
H –H

OH O—H

65. (B) 66. (C) 67. (C) 68. (C) 69. (A) 70. (C)
OH OC 2H 5 71. (B) 72. (C) 73. (B) 74. (D)
–
OC 2H 5 75. (B)
+ C2H5I As carbocation is formed so mechanism will
Anhydrous
C 2H 5OH be SN1.
So tertiary alcohol reacts fastest and by SN1.

Organic Compounds Containing Oxygen – I 361

 76. (A) Subjective Questions
Cl
CH2OH
H3C – CH2 – CH2 – C – CH3
CH3ONa CH3 84. a.
CH3OH
1-cyclopentenyl methanol

C2 H5 – CH = C – CH 3 + C2H5 CH2C = CH2 H

1
OH

6
CH3 CH3 2
b.
5 3
OCH3
4
3-cyclohexen-1-ol
+ C2 H5 – CH2 – C – CH3
4
CH3 3 5
CH 3 H
c.
77. (A) 2 1
H OH
trans-2-methylcyclopentanol
O HI
 → H OH
∆ 1
2 6
O
d. 3 5

+ 4
CH3 CH3
+
4,4-Dimethyl-2-cyclohexen-1-ol
+ CH3 CH2
85.
OH C4H7OH is an alcohol.
Cyclic isomers are
Structure Name
I− I
 →
a. OH Cyclobutanol
OH
H

Multiple Choice Questions (One or More CH2OH

b. Cyclopropylmethanol
Choice Correct) H

78. (A) and (D) CH 3

c. Methylcyclopropanol
OH
Comprehension Passage Based Questions CH 3 OH
* *
d. Cis-2-Methylcyclopropanol
79. (C) 80. (C) 81. (B) H H
(Chiral)
H
Match the Columns
OH
e. * * trans-2-methylcyclo-propanol
CH 3 H

82. (A→P,Q,S), (B→S,T), (C→P), (D→R) (Chiral)

KMnO4
Assertion and Reason Questions 86. CH3CH2CH2CHCH2CH3 
O

|
83. (C) OH

CH3CH2CH2CCH2CH3
||
O (C)
(C) is one of the products of reductive
ozonolysis. (C) has 6 carbons it means one
carbon has been lost as HCHO. Hence, (A) is

362 Organic Compounds Containing Oxygen – I

 CH3
CH3CH2CH2C − CH2CH3 
Ozonolysis
 CH — CH2OH
|| CH3
CH2 Reactions:
(A) CH3 CH3
H2SO 4
CHCH2OH C CH2
CH3CH2CH2 − C − CH2CH3 CH3 ∆ CH3
||
[O]
O CH3
C O
Ozonolysis
CH3
CH3 +
(C) CHCOOH
CH3 HCHO
( i) Hg  OAc  , H O
(A) 
2 2
 89. Molecular weight of bromo-derivative is given
( ii) NaBH4
below.
OH 0.369 × 22400
| (A) = = 123
CH3CH2CH2C * −CH2CH3 67.2
| Let bromo-derivative be RBr.
CH3 (B) Then molecular weight of R = 123 – 80 = 43
(B) has chiral carbon so it exist in two ∴ CnH2n 1  43
isomeric forms. ∴n=3
OH Thus, bromo-derivative is C3H7Br
87. Br MgBr
Mg CH3CH
CHO C — CH3 Since
et r
ethe
(A))
H
(B) (A) C3H7Br 
NaOH
 C3H7 OH
+
H Br – (A) (B )

Al2O 3 , 250°C
C 3H7 OC 3H7
+
OH2 (C )

+ + (B) C 3H7OH
Al2O 3 , 350°C C H + H O
CH3 H C — CH3 (B )
–H2O 3 6 2
CH3 (D )
H
Br–
(A) may be CH3CHBrCH3 or CH3CH2CH2Br
(I) (II)
Br
Reaction (c) suggests that isomer of (A) is
CH3
2-bromopropane.
(C)
CH3 . CH  CH2 
HBr
 CH3 .CHBrCH3
OR (D )
88. ROH + CH3MgI CH4 + Mg
I Therefore, (A) is 1-bromopropane,i.e.,
CH3CH2CH2Br.
11.2 mL of CH4 is obtained from 0.037g of ROH
22400 mL of CH4 is obtained from Reactions:
CH3 CH2 CH2Br 
NaOH
 CH3 CH2 CH2 OH
0.037 × 22400 (A) (B) Pr opan 1ol
= 74 g
11.2 Al2O 3, 250°C
CH3CH2CH2OCH2CH2CH3
Molecular weight of ROH = 74 (C) Dipropyl ether
CH3CH2.CH2OH
As ROH on oxidation gives acid of the (B )

same number of carbon atom, so ROH is Al2O 3 , 350°C CH3CH = CH2

(D) Prop-1-ene
primary alcohol, i.e., CnH2n+1 CH2OH
12n + 2n + 1 + 12 + 2 + 16 + 1 = 74 CH3 .CH  CH2 
HBr
 CH3 CHBr.CH3
n=3 (D ) Isomer of ( A )

The alcohol on dehydration gives an alkene,

H SO
which on ozonolysis gives acetone as one CH3 .CH = CH2 
2 4
 H3C −− CH −− CH3
H2O
(D )
product. Thus, alkene is given below. |
CH3 OH
C CH2 and alcohol is as follows. (E ) Propane 2-ol
CH3

Organic Compounds Containing Oxygen – I 363

 90. (x) C5H8 O does not react with Lucas reagent One mole of alcohol will give 11,200 mL of H2
appreciably at room temperature but gives at STP.
precipitate with ammonical AgNO3, thus, 1120 mL of hydrogen is obtained from 6 g of A.
(x) has terminal alkyne linkage, as well as, 11200 mL of hydrogen is obtained from
primary alcoholic group. 6
(x) on hydrogenation and then reacting with × 11200 = 60 g of (A)
1120
HI gives pentane, thus, (x) is straight chain
compound. Let the formula of alcohol be as follows.
Keeping in view of the above facts (x) may be CnH2n + 1 OH
12 × n + 2n + 1 + 16 + 1 = 60
CH2 CH2 CH2 C  CH 14n = 42
| ( x) n=3
OH Pent  4  yne  1  ol The secondary alcohol of three carbon atoms
containing only one oxygen atom is given below.
Its reaction with MeMgBr gives CH4(It has two CH CHC 6H5
acidic or active H atoms) and thus, 1 mole of
(x) will give two moles of CH4 H C OH
CH2 CH2 CH2 C  CH  2CH3MgBr  2CH4 CH3
| ( x) PBr3
CH3 — CH — CH3 CH3 — CH — CH3
OH
OH Br
 
Since 84 g x gives 2  22.4 litre CH4
(A)
CH3 CH3
(B)

CH
2  22.4  0.42
∴ 0.42 g  x  will give  224 mL CH4
84
91. Since compound (A) gives positive Lucas test
AlCl3
in 5 minutes, it is a secondary alcohol. (C)

1
ROH  Na  RONA  H
2 2

92. Compound (A) has –OH group along with unsaturation as it reacts with Na and decolourises Br2/CCI4.
(A) gives iodoform test and thus it should have CH3 CH R structure.
OH

Thus, (A) may be

CH CH CHCH3

OH
CH CH C CH3
Na
ONa
(A)
Br Br

CH CH CH CH3 Br2 / CCI4 CH CH CH CH3

OH OH
(B)

CH CHCOOH
I2/NaOH

-CHI3
(C)

364 Organic Compounds Containing Oxygen – I

 Geometrical isomers of A:
C 6H5 C H H C C 6H5
and
CH3CHOH C H CH3CHOH C H

(vi) Optical isomers of A:

CH CHC 6H5 CH CHC 6H5

H C OH and OH C H

CH3 CH3

93. Ozonolysis of B gives cyclopentanone. Thus, alkene B is

As alkenes B and C on hydrogenation yield the same product, the two alkenes differ in position of
double bond and the two alkenes are formed by dehydration of alcohol (A) without rearrangement.
So the corresponding alcohol will be as follows.
KHSO4
+
∆
OH

94. CH2 CH2OH

(i) BH3 . THF
CH3 – CH – C – CH2 CH3 CH3 – CH – C – CH2 CH3
(ii) H2O2/OH–
(A)
CH3 CH3 (B)
KMnO COOH 4

CH3 – CH – C – CH2 CH3

O3/H2O/Zn
CH3
KMnO4
HCHO + CH3 – CH – C – CH2 – CH3 CH3 – CH – CH – CH2 – CH3

CH3 O CH3 OH
(D)

O OH
H+ O
95. a.

(A)

b. CH2 CH CH3 + HBr

OH

CH CH2 CH3 + CH2 CH CH3

Br Br

(B) Major


The formation of (B) can be explained by the fact that CH CH2CH3 (benzyrlic) is more
+

stable than CH2 – CH – CH3

+

Organic Compounds Containing Oxygen – I 365

 MnO2
c. OH O

MnO2 oxidises only benzyllic and allylic 1° and 2° alcohols to aldehydes and ketones respectively.
Cl
Cl Hg(OAC) / H 2O
2

NaBH 4
OH
d. (E)
O
NaOH

(F)

Br OH –
OH
Br2 Zn i. Hg(OCOCH3)2 ii. NaBH4/OH
96.
CH2Cl2 CH3COOH THF – H2O
Br HgOCOCH3
Cyclohexanol

97. Since the acid obtained from alcohol has the same number of carbon atoms as that of alcohol,
thus, alcohol is primary alcohol, CnH2n+1CH2OH.
Gas is evolved when primary alcohol is treated with CH3MgI. At STP, 5.6 cm3 gas was evolved from
0.022 g of alcohol.
0.022
At STP, 22400 cm3 gas was evolved from  22400  88 g of alcohol
5.6
Molecular weight of alcohol = 88
Molecular weight of CnH2n+1CH2OH = 88
n  12   2 n  1  1  12  2  1  16  1  1  1  88
12 n  2 n  1  12  2  16  1  88
14 n  32  88
14n = 56
n=4
∴ Molecular formula of alcohol is C4H9CH2OH.
Since the alkene is obtained from the dehydration of alcohol and this alkene on ozonolysis, yields
2-butanone as one of the products. Thus, alkene should be as follows.
CH3

CH 3CH 2 — C CH2

Thus, the structure of alcohol should be as given below.

CH3

CH 3CH 2CH CH2OH

Thus,
CH 3 CH3 CH 3
H2SO 4 Ozonolysis
CH 3 — CH 2 C — CH 2 CH 3 — CH2 C CH2 CH 3CH2 C O + HCHO
∆
H OH
2-Methyl butanol 2-Methyl butene 2-Butanone Formaldehyde
CH3 CH3
[O]
CH 3 — CH 2 CH — CH2OH CH 3 — CH2 CH COOH
2-Methyl butanoic acid
O

PBr3 Mg/ether CH2 — CH2

98. a. CH3CH 2OH CH3CH 2Br CH3CH 2MgBr
Ethyl bromide (Y)
(X)

366 Organic Compounds Containing Oxygen – I

 +
H2O/H
CH3 — CH 2 — CH2 — CH2 — OMg Br CH 3 — CH2 — CH 2 — CH2 — OH

(Z)

CH3 CH3 CH3

– OH
dil. KMnO4 OH HIO4 O OH
CH 3
b. OH O

CH3 CH3 CH3

(X) O

H OH
+
+
H H2O CH3
99. + CH CH3
CH CH 2 CH CH3 H
Cis & trans- 2-methyl cyclopentanol

1 mol of H2 HBr
100. HC CH H2C CH 2 H3C CH2Br
(A) (B)
NaNH2
– H3C—CH 2Br i. 1 mol of H 2
HC C HC C — CH2 CH3 H2C CHCH 2CH 3
(C) (B) (D)
ii. BH3/H2O2,
–
OH
HOCH 2CH2CH 2CH 3
(E)

101. CH 3 CH3
+
H +
CH 3 — C CH2OH CH 3 — C CH2 — OH2

CH 3 CH3

CH 3 CH3 CH3
–
+ –H2 O Cl
CH3 — C CH 2 — OH2 CH3 — C CH2 — CH3 CH3 — C CH2 — CH3
+
CH 3 Cl

Ph Ph Ph Ph Ph Ph
+
H –H2 O
102. Ph C — C — Me Ph C — C — Me Ph C — C — Me

OH OH OH2 OH OH

Phenyl shift

Ph Ph Ph
+
–H
Ph C — C — Me Ph C — C — Me Ph C — C — Me

Ph O Ph OH Ph OH

103. Structural formula of alcohol produced is as follows.

CH 3

CH2 C — OH

CH 3

It can be produced as follows.

First method
CH3 CH3
CH3 +
Dry H /H2O
CH2MgBr + C O ether CH2 — C OMgBr CH2 — C OH
CH3
GI KI CH3 CH3

Organic Compounds Containing Oxygen – I 367

 Second method
O OMgBr OH
+
Dry ether H /H2O
CH3MgBr + CH2 — C CH 3 CH2 — C CH3 CH2 — C CH 3

G2 K2 CH3 CH 3

104. a. Since H contains carbon and hydrogen so it is a hydrocarbon.

b. 1 mol of H reacts with 1 mol of Br2, this indicates that H is an alkene.
c. H on ozonolysis gives acetone and acetaldehyde.
CH 3 H

CH3 — C O O C — CH 3
Acetone Acetaldehyde

CH3

Thus, the structure of H is CH 3 — C CH — CH3

2-Methyl but-2-ene

CH 3 CH3

CH3 — C CH — CH 3 + Br2 CH3 — C CH — CH3

(H)
Br Br
2,3-Dibromo, 2-methyl butane
(I)

CH 3 CH 3
Alk. KMnO4
CH 3 — C CH — CH 3 CH 3 — C CH — CH 3
(H)
OH OH
2-Methyl butan-2,3-diol
(J)

CH 3 CH3 CH 3 O
O3/CHCl3 H2O /Zn
CH 3 — C CH — CH 3 CH3 — C CH — CH3 CH 3 — C O + CH 3 — C — H
(H) Acetone Acetaldehyde
O O
O
2-Methyl butan-2,3-diol
(I)

105. Since compound (X) gives Lucas test immediately, thus, the compound is tertiary alcohol.
1
ROH  Na  RONa   H
2 2
1
1 mol of alcohol evolves mol of H2.
2
At NTP, 1120 mL of H2 is evolved from = 7.4 g of alcohol.
1 11200
 22400  = 11200 mL  of H2 is evolved from = 7.4   74 g of alcohol.
2 1120
The general formula of alcohol is CnH2n+1OH.
[Molecule has one oxygen atom]
Mol. wt. of CnH2n+1OH = 74
12 n   2 n  1  1  16  1  74
12 n  2 n  1  16  1  74
14 n  18  74
n=4

368 Organic Compounds Containing Oxygen – I

 Therefore, the structure of tertiary alcohol (X) is given below.
CH3

CH 3 C — OH

CH3
tert-butanol

The reactions are as follows.

CH 3 CH3 CH3
– CH3CH 2Br
CH3 C — OH + Na CH3 C — O Na CH3 C — OCH 2CH 3

CH 3 CH3 CH3
tert-Butyl ethyl ether
(Y)

106.
Element % At. mass No. of Atoms Simple Whole Number Ratio of Atoms
C 68.2 12 5.68 5
H 13.6 1 13.6 12
O 18.2 16 1.13 1

Thus, the empirical formula is C5H12O.

Empirical formula mass
= 5 × 12 + 12 × 1 + 1 × 16
= 60 + 12 + 16
= 88
∴ Molecular formula of (O) is C5H12O.
Since (O) gives Lucas test immediately, thus, (O) is tertiary alcohol and its structure is as given below.
CH3

CH 3 — CH 2 C — OH

CH3
2-Methylbutan-2-ol

Reactions involved are

CH 3 CH 3 CH 3
Al2 O3 O3 /CHCl 2
CH3 — CH 2 C — OH CH3CH C — CH 3 CH3CH C — CH 3
350°C
2-Methyl but-2-ene
CH 3 (P) O O
O
CH3
H2O /Zn
CH3CHO + O C — CH3
(Q) (R)
Since both are carbonyl group, so they give positive 2,4-DNP test.
(Q) is CH3CHO as it give positive Tollen’s test.
O

(R) is C H3 C CH 3.

Me Me Me
KMnO4 CrO3
107. OH OH
H ACOH
OH O
cis
Permanganate hydroxylate is a double bond that gives cis-1, 2 diol. t-alcohols are much more
difficult to oxidise than s-alcohol, since CrO3 in acetic acid is a relatively mild oxidising agent, only
the secondary alcoholic group in the diol is attacked.

Organic Compounds Containing Oxygen – I 369

 +
108. H2C CH CH CH3
H
H3C
+
CH CH CH 3
Hydride shift
H3C CH2
+
C CH3

C 6H5 C 6H5 C 6H5

3-phenyl-2-butene H2O
+
–H
OH

H3C CH2 C CH3

C 6H5
2-phenyl-2-butanol
In this reaction, hydration gives an intermediate, which undergoes a hydride shift. Although phenyl
(—C2H5) is a better migrating group than –H but migration of –H occurs which lead to a more stable
3° benzylic carbocation.

109. Element Percentage Relative Number of Atoms Simplest Ratio

C 76.6 6.38 6
H 6.38 6.38 6
O 17.02 1.06 1
∴ Empirical formula of (A) = C6H6 O;
Empirical formula weight = 94
Molecular weight of (A) = 2×47 = 94
∴ Molecular formula of (A) is C6H6 O
(A) gives characteristic colour with FeCI3 and thus, it has phenolic group. Therefore, (A) should be
C6H5 OH.
Reactions:
OH OH
NaOH + CO2 OH H+
∆
COONa COOH
Phenol (C)
(B)
Sod.salicylate salicylic acid

OH OOCCH3
CH3COCI

COOH COOH
(C) (D)
Pain killer
(Aspirin)

110. The given reactions suggests that (A) is phenol.

OH OH OH
CHO
CHCl3 + KOH
+
Reimer-Tiemann
reaction
(B)
(A) CHO
(C)

Zn dust

COOH CHO
Sodaline [O]

(F) (E)
(D)

370 Organic Compounds Containing Oxygen – I

111. Since (P) gives characteristic colour with neutral FeCl3, thus, P has phenolic group.
(P) on treatment with Br2 gives C7H5OBr3. Thus, –CH3 group in (P) should be at meta position, then
only tribromo derivative can be obtained.
OH

Thus, P is m-cresol
– +
CH3 O Na

m-Cresol being weak acid do not react with NaHCO3 but dissolves in NaOH to form
CH3
OH OH
Br Br
Br2

CH 3 CH 3
Br
(Q)

O I I
112. (A) + 2HI (B) + HI

O OH I
I
I
O HO OH
(C) + HI (D) + HI
O

12 0.308
113. Percentage of C =   100  77.77 Relative Number Simplest
14 0.108 Element %
of Atoms Ratio
2 0.072
Percentage of H =   100  7.40 C 77.77 6.48 7
18 0.108
Percentage of O = 100 – (77.77 + 7.40) H 7.40 7.40 8
= 14.83 O 14.83 0.93 1
Empirical formula of (A) = C7H8O
Since (B) gives C7H5OBr3 and (B) is isomer to
(A), the molecular formula of (A) and (B) is
C7H8O. (A) is insoluble in NaOH and NaHCO3 .
So (A) is
O CH3

O CH3 OH

+ HI + CH3 I
(C)
(A) (Soluble in ethanolic AgNO 3)
(D)
(Soluble in NaOH)

Organic Compounds Containing Oxygen – I 371

 OH

Since (B) is soluble in NaOH and gives (E) C7H5OBr3 with Br2 water, (B) is because
only meta position can provide tribromoderivative.
CH3
OH OH

Br Br
Br2 water

CH3 CH3
(B)
Br
(E)

CH 2CH 3 CHBrCH3 CH CH2

AlCl3 NBS alc. KOH

114. + CH3CH2Cl

(P) (Q) (R)

H
KO
aq.
OH

CH CH3 CH CH2 CH3 — CH OCH

i. Hg(OCOCF 3) 2
ii. NaBH4 CH3
+

(S) (R) (T)

115. C H OH , C2H4
2 5
ethyl alcohol ( A ) (B)

116. C2 H5 OC2H5 2C2H5I 2C2H5OH

X Y Z

HPh
3C
H H3C
HI
117. a. CH3CHO b. MeO CH O HCH 3 c. CH(OH) + CH3 I
(excess)
H3C H3C
Ph

OH

118. CH3 CH CH3 , CH3CH CH2,CH3CH CH,CH 3COCH 3

A B C D

OH

119. a. b.

OH

372 Organic Compounds Containing Oxygen – I

120. A – CH3OH (Alcohol, Methanol) 123. HC C CH 2CH 2 CH 2OH
B – CH3COOCH3 (Ester, Methyl acetate)
124. trans-2-butene
C – HCHO (Aldehyde, Formaldehyde)
D – HCOOH (Acid, Formic acid) 125. CH CH 3 , COOH
E – HCONH2 (Amide, Formamide).
D OH E
OH
CHO CH3 CH 3
121. Fuse with NaOH;
126. HC C C OH,CH3CH 2 C OH

OCH 3 OH CH2CH 3 CH 2CH 3

A B

CH2CH 3
122. , CH3I, ,
C
HO H
(Anisole) D 127.
HO H
A

OH CH2CH 3
OH
Z
Br Br
, O
CH3 CH3
CH 3 CH3 128. , C
(m-cresol) C H
B Br (X)
(C7H5OBr3) O
E (Y)

Organic Compounds Containing Oxygen – I 373