benzene

2.4-diarboxylic
acid

CH20COR CHzOH
I I
CHOCOR + 3NaOH-------4 + CHOH 3RCOONa
I I

Terminal Questions

1) a) CH3CH2CHCH2CH3,secondary; b) CH3 -CCH2 -OH, primary;

I I

2) b.p. a) propanol b) 1-butanol c) 2-butanol d) p-n~trophanol

Solubility
in water propanol I-bulanol 2-propanol pnitrophenol
3)
4)
5)
See subsection 12.6.1

a) (CH3)3COH+ HCl
b) C2 HsOH -
See subsection 12.6.2

Na
- (CH3)3CCI + H20
C2HPNa + bH.1

2-hydroxybcozoic acid
(solialic acid)

6) Lucas reagent (HCYZnC12)is used to differentiate primary, secondary and tertiary

alcohols. Tertiary alcohols react immediately upon shaking with lucas reagent in a
test tube. Secondary alcohols react in 2,3 minutes and primary alcohols do not
reaci with reagent unless the mixture is heated.
 Structure

13.1 Introduction
Objectives
13.2 Classification
13.3 Preparation of Ethers
Preparationof Open Chain Ethers
Preparationof Epoxides
13.4 Properties of Ethers
Physical Properties
Spectral Properties
Chemical Properties of Open Chain Ethers
Chemical Properties of Epoxides
13.5 Crown Ethers
, 13.6 Industrial Uses
13.7 Sulphur Analogues of Alcohols and Ethers
Preparation of Thiols and Sulphides
Properties of Thiols and Sulphides
13.8 Summary
13.9 Terminal Questions
13.10 Answers

13.1 INTRODUCTION

In the previous unit, while discussing the chemistry of alcohol, it was pointed out that
dialkyl derivatives of water are called ethers. In this unit we shall take up the
chemistry of ethers.
In this unit we shall first take a look at the different types of ethers and give you their
preparation. We shall then consider their structure, physical, spectral and chemical
properties and industrial uses. We shall also touch briefly on a special type of
macrocyclic (i.e. large ring) compounds, the crown ethers. Finally, we shall take up
the chemistry of sulphur analogues of alcohols and ethers.

Objectives
After studying this unit, you should.be able to:
list different types of ethers such as open chain ethers, epoxides and crown ethers,
outline the preparation of open chain ethers and epoxides,
explain the physical and spectral properties of ethers,
describe the chemical properties of open chain ethers and epoxides,
describe the crown ethers,
state the different industrial uses of ethers, and
describe the preparation and properties of thiols and sulphides.
 Ethers and Sulphur Analogues of
13.2 CLASSIFICATION Alcohols and Ethers

Ethers can be considered as derivatives of water. They can also be considered as alkyl
derivatives of alcohols. Like water and alcohols, ethers contains an s$ hybridised
oxygen atom. But, in an ether the oxygen is bonded to two carbon atoms. The groups
bonded to the ether oxygen can be alkyl, aryl, ethenyl, or any other carbon containing
groups. Aliphatic ethers may be simple or symmetrical in which both the alkyl groups
are the same or mixed i.e. unsymmetrical in which case the two alkyl groups are
different, e.g.,

diethyl ether methyl ethyl ether

(ether) (methoxy ethane)

simple ether mixed ether

Aromatic ethers may be regarded as derivatives of phenol and are also divided into
two groups, the alkyl aryl ethers and diaryl ethers:

alkyl aryr ethers diary1 ethers

or phenolic ethers

where, R = alkyl group

Ar = aryl group

Ethers can be either open chain or cyclic. When the ring size (including the oxygen
atom) is five or greater, the chemistry of the cyclic ether is similar to that of an open
chain ethers. Three membered cyclic ethers are called oxiranes (IUPAC name), which
are often known as epoxides. Because of Baeyer strain associated with small rings,
epoxides are more reactive than other ethers.

oxirane tetra hydmfuran 1,4dioxane

(ethylene oxide) (THF)
epoxide

Large ring systems with repeating -OCH2CH2- units are called crown ethers. These
compounds are valuable reagents which can be used to help dissolve inorganic salts in
organic solvents. Crown ethers are named as Xcrown Y, where X=the total number
of atoms in the ring and Y=the total number of oxygen atoms in the ring. For
example,

18-Cmwnd

A crown ether with a total number of atoms 18 and 6 oxygen atoms in the ring
Derivatives of Hydrccarbo~w-I Ethers occur widely in nature, some examples of naturally occurring ethers are:

OCH3
O 7
<
+OCH3

CHzCH =CH2
Q CH=CHCH3 CH2CH=CH2 CHO
Gusicol eugenol anethol safrole Vanillin
(kh-wwd (oil of (aniseed (camphol (vanilla
m) cloves) oil) oil) been)

13.3 PREPARATION OF ETHERS

In this sections, we will discuss first the preparation of open chain ethers and then the
preparation of epoxides.

13.3.1 Preparation of Open Chain Ethers

Ethers are commonly prepared from alcohols. There are two methods.
i) Acid catalysed dehydration
ii) Nucleophilic displacement (Williamson ether synthesis)
Let us discuss these preparative method briefly.

i) Acid catalysed dehydration

In Unit 7 we described the conversion of alcohols to alkenes in the presence of
sulphuric acid. When an alcohol is reacted with H2S04,a series of reversible reactions
occur under different experimental conditions. Which reaction product predominates
depends on the structure of the alcohol, the relative concentration of reactants, and
the temperature of the reaction mixture. For example.
273 K R - O S a O H + R--OS& 0-R + Hz 0
aUryl hydrogen dialkyl
sulphate sulphate

R-0-R + H20
either
alkenes + H20
alkenes + Hz0
R-OH + H2s04.
aecmdary and
teniary alcohol

As shown above primary alcohols give alkyl hydrogen sulphate and dialkyl sulphate at
low temperatures, symmetrical ethers at moderate temperature and alkenes at high
temperature. Tertiary alcohols and to a large extent, secondary alcohols yield alkenes.
Industrially, diethyl ether is prepared by this method from ethanol in the presence of
sulphuric acid. But in the laboratory, as might be expected, we get a large number of
possible products, and this ethod is, therefore, seldom used for the synthesis of
ethers. 9
U) WWunson ether synthesis
Ethers are also prepared by Williamson's synthesis in which alcohols are employed as

-
starting materials. One alcohol is converted to alkyl halide (R-X), another alcohol is
converted to sodium or potassium alkoxide or then two products are heated together.
R-ONn + R-X R-0-R + Na+X-
sodium alkyl symmetrical
alkoxide halide ether
 Ethers and Sulphur Analogues of

..
R-6-R +
..-
..
:x:
Alcohols and Ethers

The mechanics of the reaction is SN2,which we have discussed in kletail in Unit 11.
As already mentioned the tendency for alkyl halides to undergo this reaction isp > Secondary and tertiary alkyl
see > tert. halides lead to alkenes, while aryl
and ethenyl halies do not undergo
This method can also be used to prepare phenolic ethers: SN2reactions, therefore, they do
not give ethers with alkoxides or
Ar-0-Na+ + R-X-Ar-0-R + Na+X- phenoxides.
sodium albyl phenolic ethers
phenoxide halide or alkyl aryl ether

Before considering the properties of ethers, try the following SAQ.

SAQ 1 . /

Predict the major products of these reactions?

warm
- .
%

a) CH3CH20H+H2S04 413.

heat
+
b, CH~CH~O-N~'
heat
c> C H ~ O - N ~++(CH,),CCI >-
heat
d) n D N a ' + CH3Br +
w
13.3.2 Preparation of Epoxides

RCH =CHR+RrCOOOH
alkene peracid .
-
Epoxides are obtained by the reaction of alkenes with peracid, e.g.,

inether
/ 0\
RCH- CHR
or trichloro
+R-COOH

epoxide
methane

They are also prepared by the reaction of chlorohydrin with alkali, e.g.,

HOCH2CH2Cl+KOH ---r /O\ + KC1 + H20

Z-chloro 1-ethanol CHZ-CHz
chlmhydrin
oxirane
(ethyleneoxide)

Ethylene oxide is manufactured by the silver-catalysed oxidation of ethenes with

oxygen.

2CH2=CH2+02
ethene
- A"
523 K
/O\-CH2
CHz
oxirane '
(ethylene oxide)

13.4 PROPERTIES OF ETHERS

Before studying the reactions of open chain ethers and epoxides in detail, let us first
take up their physical and spectral proposition.

13.4.1 Physical Properties

Ethers are polar compounds with dipole moment 3 . 9 I~O - ~ Cm (for diethyl ether).
But they are not as polar as water, 6 . 0 I~O - ~ Cm and alcohols, 5 . 7 I~O - ~ C
m (for
methanol). Ethers have lower boiling points as compared to those of alcohols
containing the same number of carbon atoms. This is due to the fact that, unlike
alcohols, ethers cannot associate through hydrogen bonds in the pure state because
they have no hydrogen attached to the oxygen. However, ethers can form hydrogen
bonds with water, alcohols and phenols. Because of hydrogen bonding with water,
ethers show a considerable solubility in water.

R\ '0:
------ ..
H-O
2 H
'
We are summarising the physical properties of some ethers in Table 13.1.

Table 13.1: Physical properties of some ethers

Name Formula BPS Density Solubility in
kgdm-3 H20
a1293 K
Dimethyl ether CH30CH3 249 gas miscible
Diethyl ether C2HSOC2HS 307.6 0.71 8 g1100 cm3
Methyl phenyl ether (anisol) C6H5-OCH, 427 - -
Tetrahydrofuran (THF) 339 0.89 miscible

Oxirane
/O\
(ethylene oxide) CH2 -CH? 286.5 8.88 miscible
- - -- - - - - - -
(at 283 K\
- - - -

Before studying the spectral properties of ethers try the following SAQ.

SAQ 2
To what effect can you attribute water solubility of ethers?

13.4.2 Spectral Properties

Like alcohols, ethers show the C-0, stretching vibration at 1060-1300cm-' range in
ir spectra. The 0 - H band characteristic of alcohol is, of course, absent.
In the nmr spectra, as in the case of alcohols, the oxygen atoms cause deshielding of
the protons on adjacent carbon (aprotons) and shifts their absorption downfield.

p = 1 . 5 pm
6=0.9 ppm 7 1 r 6=0.9pprn
CH3CH2CH20CH2CH2CH3
ts=,4ppm f

13.4.3 Chemical Properties of Open Chain Ethers

Ethers are quite unreactive and behave more like alkanes than like organic
compounds containing functional groups. The bond between carbon and oxygen in a\
ether is called the ether linkage. This ether linkage is not affected by bases, oxidising
agents and reducing agents. The oxygen atom in ethers can readily accept protons
(base in Bronsted concept) and it also can be electron-pair donor (Lewis base). On
treatment with acids, ethers give oxonium salts:
+.
R -0:+ &I- R -0: HCI-
I
R
oxonium salt
 .t
R-O:+BF~ R-O:BF?
I I
R R
oxonium salt

Further treatment with an alkyl fluoride gives a tertiary oxonium salt, trialkyl
fluoroborate.

R20+:BF3:+RF ~ ~:BF4-
0 '
trialkylfluoroborates

The products of the above reaction, i.e. the trialkyl fluoborates are powerful
alkylating agents in many reactions.
On heating ethers with dilute sulphuric acid under pressure alcohols are obtained:
H2S04
R-0-R+H20 2R-OH
pressure
C

When they are heated with a strong acid (usually HI or HBr), ethers do undergo
substitution reactions. This is the most important reaction of ethers. In this reaction,
cleavage of the ether linkage (C-0) takes place. For example, when heated with HI
an ether yields an alcohol and an iodoalkane. Under the reaction conditions, the

R-0-R+HI

R-0-H+HI ----,
-
alcohol formed in turn reacts with HI to give iodoalkane and water.
heat
R-I + R-OH
iodoalkane alcohol
R-I+H20
We can write the net reaction as
heat
R-0-R+2HI h 2RI + H20
403-423 K
Cleavage of ethers may also be accomplished by the use of concentrated (48%)
hydrobromic acid.
CH3
I
CH3--~~--0-CH-CH3
CH3
I

2-(1-methyl ethoxy) propane

(isoprcpyl ether)
-48% HBr
403 K
CH3
2CH3 -CH - Br
I

(Zbromopropane)
(~sopropylbromide)

Ether cleavage with HI or HBr proceeds by almost the same path as the reaction of
alcohol with HX: protonation of the oxygen, followed by SNlor SN2reaction.

pmtonated S& traositioa state

after affecting a chemical transformation at another site in the molecule regenerating

through treatment with concentrated hydriodic acid.
Aromatic ethers, such as anisol, yield the alkyl iodide and phenol, not iodobenzene
and methanol, because s$-hybridise carbon does not under go reaction by an SN1or
SN' path.
Derivatives of Hydrocarbons-I

The &isel procedure for estimation of the number of methoxyl (CH30-) or ethoxyl
(CYCH20-) groups in alkpl aryl ethers consists of ether cleavage with excess HI,
followed by distillation of volatile iodomethane or iodoethane from the reaction
mixture. Then, the iodoalkanes are treated with an ethanolic solution of silver nitrate,
and the silver ,iodideso formed is weighed.

SAQ 3
In Section 13.2, we mentioned the structures of vanillin, a naturally occurring ether.
Now, write the equation for the reactions that would occur in the determination of the
number of methoxyl groups.

An epoxide ring cannot have 13.4.4 chemical Properties of Epoxides

nonnal sp' bond angles of 109";
instead, the inter nuclear angles As stated earlier epoxides are highly reactive compounds. The characteristic reaction
are 60", a geometric requirement of epoxides is nucleophilic substitution reactions. In this reaction, ring opening takes
-
of the three-membered rinn.The
orbitals forming the ring bonds are
place which can occur either under alkaline or acidic reaction conditions. General
reaction can be written as
inca~ableof maximum overlap.
Theiefore, epoxide ring are -
OH
strained. The polarity of the
C-0 bond, dong with the ring
>%< I
strain, contributesto the high R-CH-CH-R + ~'fi: R-CH---CH-R
reactivity of epoxides compared to
the reactivity of other ethers

Like other ethers, epoxides undergo carbon-oxygen bond cleavage when treated with
'
f
6
C0
?
)
$;
-,I - an acid. However, because of their high reactivity much milder acidic conditions are
C sp3 carbon , employed than for cleavage of open chain others.
polar and s ~ n i ~ ~ c d

oxirane 1, 2ctbancdiol
(clhylcnc glycol)

.With concentrated acid, e.g., HCl, chlorohydrins are obtained:

oxiranc Z-chloro-1ethanol

In Base
Unlikd open chain or 5- or higher membered cyclic ethers epoxides react with bases,
e.g., NaOH, NaOCH3 to give 1,Zethanediol (ethylene glycol) and 2-methoxyethanol,
respectively.
011 011
/O\ I I
CI.12-CHI + H20 l
i; Ct12-C112
oximnc 1, 2-ctlhancdiol
Epoxides are used as intermediates in synthesis. The reaction of epoxides with Ethers and Sulphur Analogues of
Grignard reagent has already been mentioned in Unit 11. Oxirane with Grignard I Alcohds Pnd Etbers
reagent gives primary alcohol:

/O\ H'/H~ 0
RMgX + CH2 -CH2 RCHzCH2 -OMgX _____,
oxirane

RCH2CH2 - OH + M
primary alcohol

On heating oxirane ethanal is formed:

/O\
CH2-CH2
oxirane
- heat
CH3CHO
primary alcohol

Reduction with lithium aluminium hydride converts epoxides into alcohols, e.g.,

/"\ LiAIH4
RCH-CH2 h RCHOHCH3
oxide alcohol

SAQ 4
How would you prepare 1-butanol from the Grignard reagent C2H5MgBr?Show the
steps involved in this synthesis.
.
..............................................................................................................

13.5 CROWN ETHERS

As mentioned earlier, crown ethers are cyclic ethers with structure consisting of
repeating -OCH2CH2- units. They are polymers of 1 , 2 ethanediol (glycol).

The unique feature of crown ether is that they can chelate metal ions and give metal
complexes which are soluble in nonpolar organic solvents. In this form the crown
ether is referred to as the host, while the metal ion is called the guest. For example,
purple benzene is a reagent in which KMn04, complexed by 18-crown-6, is dissolved
in benzene.
k d v d v 5 d fClydmrbzrn~I Some of the crown ethers are involved in the transport of ions across biological
membranes.

13.6 INDUSTRIAL USES

Ethers are widely used as solvents for oils, fats, gums, resins, etc. Diethyl ether is used
as a refrigerant. It is used as an solvent for extraction of organic matter,-as an
anaesthetic in surnerv and in the laboratory for preparation of Grignard reagents. It is
known that the Grignard reagents coordinate with ether and in the ether solution it
exist as: RMgX(OR'2)2 (as dietherates). Methy tert-butyl ether and diisopropyl ether
are used as an anti-knocking agent instead of the highly toxic tetraethyl lead. These
compounds increase the octane number when mixed with petrol.
In the presence of air and light, ether forms peroxide, CH3CH(OOH)OC2H5,which is
highly explosive. To prevent the formation of peroxide either, some ethanol or a small
amount of cuprous compound, e.g., cuprous oxide is added.
Crown ethers have great advantages in synthetic organic chemistry. One is that an
ionic reagent can be dissolved in an organic phase where it can react with a
water-insoluble organic compound. A second advantage is that the nucleophilicity of
an anion such as CN- or CH3COO-is greatly enhanced in nonpolar solvents, where the
anion is poorly solvated, or naked. An example of how a crown ether increases the
rate of a substitution reaction is preparation of the benzyl methyl ether shown in

0 CH2Br + V~CH, -0
acetonitrite which does not dissolve ionic compounds.

cHCN
2 hr
CH20CH3. + K+B;

5% yield with no crown ether.

1@~% yield with 18aown-6.

13.7 SULPHUR ANALOGUES OF ALCOHOLS

AND ETHERS

In Unit 12 and in this unit we have described the chemistry of alcohols and ethers. In
this section we shall take a look at the chemistry of sulphur analogues of alcohols and
ethers.
The divalent sulphur compounds can be regarded as the sulphur analogues of the
corresponding oxygen compounds. The sulphur analogue of an alcohol is called an
alkane thiol or simply thiol, or by its older name mercaptan. Similarly sulphur
analogue of a phenol is called an aromatic thiol or thiophenol. The -SH group is
called a thiol group.
CH3
..
CH3 - $H CH3 CHI - SH CH3CH2kH-.$-I
melhanelhiol elhanelhiol 2-bu~ane~hiol

.
Thiophenol

The sulphur analogue of an ether is called a sulphides or thioether (R-S-R).

CH3-S-CH3 CH3CH2CH2-S-CH2CH3
dimethyl sulphide ethyl propyl sulphide

Let us study the preparation of thiols and sulphides.

-13.7.1 Preparation of Thiols and Sulphides Etbers .ad Sulphur analog^
.-.. -.
Thiols can be prepared from alkyl halides by displacement with hydrosulphide ion,
HS- in ethanol solution.

-
C2HSOH
CH,-SH +Na+I-
methanethiol

Good yields are obtained only if an excess of hydrosulphide is used because of the
equilibrium:

The thiol anion produced by this equilibrium is itself a good nucleophile and can react
with the alkyl halide to give the corresponding sulphide.
CH3-SYCH3-I CH3-S-CH3+I-
dimethyl
sulphide

The use of a large excess of hydrosulphide makes its reaction with the alkly halide
more probable and maximises the yield of a thiol.

(CH3)3CMgBr+S8 - (CH3)3CSMgBr -
Thiols can also be prepared by the reaction of Grignard reagent with sulphur.
HCI
(CH3),C-SH+MgBrCl
2-methyl-
I
Thiols may be prepared in good yield by alkylation of the highly nucleophilic thiourea
followed by basic hydrolysis:

S-alkylisothioumnium
bromide
A

Sulphides are prepared by a variation of the Williamson synthesis.

CH3CH,-SH + NaOH CH3CH2-S-Na+ + H20

-
ethanethiol

CH3CH2-S-Na+ + CH3Br CH3CH2-S-CH3 + NaBr

ethylmethyl sulph~de

13.7.2 Properties of Thiols and Sulphides

I
The most characteristic property of the thiols and sulphides is their disagreeable
odour. The human nose is very sensitive to these compounds and can detect their
presence at levels of about 0.02 parts thiol to one billion parts air. For this reason,
methyl sulphide is added to natural or L.P. gas as an odourant for safety precaution.
Natural o r L.P. gas is itself odourless.

Sulphur is less electronegative than oxygen and its outer electrons are more diffuse,
therefore, sulphur atoms form weaker hydrogen bonds then oxygen atoms. For this
reason, H2S has a lower boiling point (b.p. 212 K) than water (b.p. 373 K) and thiols
have lower boiling points than their analogous alcohols (see Table 13.2). 75
 Derivatives of Hydrocarbons-I Table 13.2: Comparison of the boiling points of thiols and alcohols

Compound Boiling point K

CH3-SH 279.2
CH3-OH 338.0

Because of the relatively weaker hydrogen sulphur bond, thiols are more acidic than
water, with pK, values ranging from 9 to 12. Unlike alcohols which can in
deprotonated only by strong base such as sodium metal or NH*,thiols can be ionised
by the hydroxide ion.
CH3CH2-SH + OH- > CH3CH2-S- + H20
stronger stronger
acid than base than
H20 RS-
Chemical Reactivity of Thiols and Sulphides
Thiols and sulphides can react in ways that are very similar to those of the
corresponding oxygen analogues. Thiols and sulphides react more rapidly than their
oxygen analogues because the sulphur atom in thiols and sulphides is more
nucleophilic than the oxygen atom in alcohols. The possible explanation for greater
nucleophilicity of sulphur analogues is that the outer electrons on sulphur atom is
more diffused because of the larger size of sulphur atom as compared to the smaller
oxygen atom nucleophiles. Therefore, the electrons of sulphur readily available for
substrate (electrophile) in a reaction.
Thiols react with alkyl halides by the normal SN2mechanism in the presence of a base
to give sulphides.
NaOH
R-SH + R'-Br R-S-R' + NaBr + H 2 0
sulphide
I Mechanism
. \

1 R-SH t OH- R-S t H20

R-S
nt o
R'-Br
S N ~
> R-S-R' t Bf

Similarly, sulphides react readily with alkyl halides by the SN2mechanism to produce
trialkylsulphonium salts.

..
CH~--S-CH~
n t
p.
CH3-I:
CH3,
CH( '
..
S+-cH3 :.I-

trimethylsulphonium iodide
Like their oxonium analogues, sulphonium salts are subject to nucleophilic attack at
carbon, sulphide functioning as the leaving group:

~6 t
n P. CHI- S(CH3)2 ..
HOCH~ t s.. (CH3)2

Thiols are readily oxidised by mild oxidking agents such as I2 to disulphides. The
disulphide bond is weak is easily reduced by either tin or zinc in dilute acid to give

oxidation
R-S-S-R
reduction a disulphide
 The disulphide can be oxidised to a sulphoxide or a sulphone depending on the Ethers and Sulphur Analogues of
reaction conditions. For example, 30% hydrogen peroxide in the presence of an acidic Alcohols nnd Ethers
catalyst oxidises a sulphides to sulphoxides at 298 K or to sulphones at 373 K.
0 The disulphide link is an
important structural feature of
some proteins, like insulin. The
disulphide bond helps hold protein
chains together in their proper
CH3 SCH3 + Hz02
1- 373K
dimerhl sulphoxide @MSO)
0
II
shapes.
Dimethyl sulfoxide (DMSO) is a
unique and versatile solvent. It has
a high dielectricconstant. It is a
powerful solvent for both
inorganic ions and organic
Compounds. Reactants often have
dimethyl sulphone enhanced reactivity in DMSO
compared to that in alcoholic
The unique behaviour of sulphoxide is due to the presence of the empty'dorbital in solvents. BMSO readily
the sulphur atom. penetrates the skin and has been
used to promote the dermal
SAQ 5 . absorption of drugs.
Complete the following equations:

13.8 SUMMARY
,
What we have studied in this unit can be summarised as follows:
Ethers can be prepared by the reaction of alcohols with sulphuric acid at moderate
temperatures or by the reaction of an alkoxide (RO-) or phenoxide (ArO-), with
an alkyl halide (Williamson ether synthesis).
Epoxides can be prepared by the reaction of aper acid (RCOOOH) with an alkene
or by the reaction of chlorohydrin with alkali.
Ethers are less reactive than alcohols and they undergo only ether cleavage reaction
when heated with HBr or HI.
I
Epoxides are more reactive than other ethers and undergo ring opening with acids
or with bases or with Grignard reagents.

b
Crown ethers are cyclic ethers that are used to chelate metal ions.
Cyclic ethers are intermediates in many synthetic reactions. Most ethers are used as
solvents.
Thiols and sulphides are similar to their oxygen analogues in many of their
reactions, through they are stronger nucleophiles.

13.9 TERMINAL QUESTIONS

1) Complete the following equations:

a) ROH + H2S04
b) C&O-Na + C2HSBr
-
-
273 K

sodium phenoxide
D a i v s t l v s of Hydromskb-1

heat

2) Write equation to show how you would prepare the following compound.

3) HOWare the methoxy and ethoxy groups estimated in a compound'!

4) Give two important features of the crown ethers.
5) Why one sulphur analogues of alcohol and ethers more nucleophilic? Give two
examples of their nucleophilic reactions.

13.10 ANSWERS

Self Assessment Questions

warm
1) a) CH3CH20H + H2S04 -----., CH3CH2-0-CH2CH3 + H20
excess of diethyl ether
alcohol

heat
b) +
CH~CH~O-N'~ (/w\$- Br no reaction
heat
C) CH30-Na+ +(CH3),CC1 P CH~--C=CH?
I

-0
CH3
2-methyl propene

d, 0 0-N; + CHar
heat
o-cH3

methyl phenyl ether

(anisole)

2 ) , Water solubility of ether can be attributed to hydrogen bonding between oxygen

of ether with water.

heat

HI

CHO CHO
Vanillin no hrrthcr reaction

4) 1-Butanol can be obtained by the reaction of Grignard reagent QHSMgBr with

- -
oxirane and followed by hydrolysis with water.

jo:?
CH2-CHI.
n- + %H&B~
ether
CH3CH2CH2CH20MgBr
Hi/Hz0

CH3CH2CH2CH20H + HOMgBr
 Ethers and Sulphur Analogues of
Alcohols and Ethers
dimethyl sulphoxide

b) 0 SH-
NaOH
0 SNa + CH3CH2-1 >- - 0 s- + NaI

c') C,H5-SH + I2 R-S-S-R + 2 HI

a disulphide

Terminal Questions
273 K
1) a) R-OH+H2S04 R-OS020H + R-OS020-R+H20
alkyl hydrogen dialkyl sulphate

b) C6H5-ON, + C2H5-Br
sodium phenoxide
-
sulphate

C6H5-0-C2H5
ethylphenyl ether
+ NaBr

c) heat

) 0 CHzMgCI +
.
?)!
/ \
CH2 -C&
1. diethyl ether
2. H'IHS >
Oxirane 3-phenyl pmpanol
magnesturn
chloride

3) Methoxy or ethoxyl groups in an organic compounds are estimated by the Zeisel

method. In this method the organic compound is first heated with excess of HI
followed by distillation of volatile iodomethane or iodoethane from the reaction
mixture. Then the iodomethane or iodoethane is treated with ethanolic solution
of silver nitrate, and silver iodide so formed is weighed.

4) i) Crown ethers can chelate metal ions and give metal complexes, which are
soluble in non-polar organic solvents.
ii) Nucleophilicity of certain anions is also increased by the crown ether and
hence increased the rate of reaction of such anions.
5) See section 13.10.2.
UNIT 14 ALDEHYDES AND KETONES

Structure

14.1 Introduction
Objectives
14.2 Preparation
General Methods of Preparation of Aldehydes and Ketones
Specific Methods of Benzaldehyde
Industrial Preparations of Aldehydes and Ketones
14.3 Physical and Spectral Properties
Nature of the Carbonyl Group
Physical Properties
. Spectral Properties
14.4 Reactions of Aldehydes and Ketones
Addition Reactions
Reactions of a Hydrdgen
Oxidation
Reduction
Specific Reactions of Methanal
specific Reactions of Aldehydes
Specific Reactions of Ketones
14.5 Reactions of Aromatic Aldehydes and Ketones
Benzaldehyde
Phenylethanone

14.6 Industrial Uses

14.7 Lab Detection
14.8 Summary
14.9 Terminal .Questions
14.10 Answers

14.1 INTRODUCTION

In previous units you have studied the chemistry of alcohols and ethers. In this unit we
take up aldehydes and ketones. Both these classes of organic compounds have a
carbonyl group, >C=O. A ketone has two alkyl (or aryl) groups attached to the
carbonyl carbon, while an aldehyde has at least one hydrogen atom attached to the
carbonyl carbon. The other group in an aldehyde can be alkyl, or aryl
0 0 0
II II II
aldehydes H-C-H R-C-H Ar-C-H

0 0 0
carbonyl group
II II .I1
ketones R-C-R. Ar-C-R Ar-C-Ar

The remarkable reactivity of the carbonyl group makes the chemistry of aldehydes
and ketones the backbone cif synthetic organic chemistry. The double bond between
the carbon and oxygen atoms in these compounds serves as a model for the reaction of
many other functional groups containing ?r bonds between dissimilar atoms. Although
the reactions of carbonyl compounds are quite simple their synthetic utility is
enormous. Additions and substitution reactions are of major interest. In this unit you