Block 3

Unit 9 Carboxylic Acid
UNIT 9
CARBOXYLIC ACIDS
Structure
9.1 Introduction Reaction
Expected Learning Outcomes Reduction
9.2 Structure and Reactivity Decarboxylation
9.3 Physical Properties Conversion to Alkanoyl Halides
9.4 Preparation of Carboxylic Acids 9.6 Industrial Uses of Carboxylic
Acids
9.5 Reactions of Carboxylic Acids
9.7 Summary
Esterification
9.8 Terminal Questions
Conversion to Amides
9.9 Answers
Hell-Vohlard-Zelinsky
9.1 INTRODUCTION
You might have come across some carboxylic acids in your daily life such
as formic acid, acetic acid and tartaric acid. All these acids belong to a
class of organic compounds, called carboxylic acids. The carboxylic acids
O
are the compounds which contain the carboxy ( C OH ) group and can
O
and can be represented either as RCOH or RCOOH. The carboxylic acids
not only form an important class of organic compounds but are also the parent
compounds of a large group of compounds called the functional derivatives of
carboxylic acids. The carboxylic acid derivatives can be further classified as
acid halides, acid anhydrides, acid amides and esters. These classes of
compounds will be discussed in Unit 10. The carboxylic acids also play an
important role in various biological processes. In Unit 13, you will study about
some such acids.
Expected Learning Outcomes

After studying this unit, you should be able to:
 give structures and names of the carboxylic acids and explain their
reactivity;
5
Block 3 Carboxylic Acids, their Derivatives and Amino Compounds
 predict and correlate the physical properties such as melting point,

boiling point, solubility and spectral characteristics of carboxylic acids
with their structures;
 list various methods of preparation of carboxylic acids;
 outline the synthesis of various carboxylic acids using the above

methods starting from appropriate starting materials;
 explain various reactions of carboxylic acids; and
 describe the importance and uses of carboxylic acids.
9.2 STRUCTURE AND REACTIVITY

As you know, the carboxylic acids contain a carboxy group linked to the
carbon chain. The study of their nomenclature is very interesting. Nowhere
else in organic chemistry, the common names are so prevalent as they are
among carboxylic acids. Some examples are listed in Table 9.1 along with
both their common and IUPAC names. Before studying the chemistry of mono
carboxylic acids you can refresh your memory by going through the list of
carboxylic acids.
Table 9.1: Some Carboxylic Acids
Structure IUPAC Name Common Name

HCOOH Methanoic acid Formic acid
CH3COOH Ethanoic acid Acetic acid
CH3CH2COOH Propanoic acid Propionic acid
CH3(CH2)2COOH Butanoic acid Butyric acid
CH3(CH2)3COOH Pentanoic acid Valeric acid
CH3(CH2)4COOH Hexanoic acid Caproic acid
Aliphatic acids having CH3(CH2)5COOH Heptanoic acid Enanthic acid
14 or more carbon CH3(CH2)6COOH Octanoic acid Caprylic acid
atoms are also
referred to as fatty CH3(CH2)7COOH Nonanoic acid Pelargonic acid
acids because many CH3(CH2)8COOH Decanoic acid Capric acid
of them were first
obtained by the CH3(CH2)10COOH Dodecanoic acid Lauric acid
hydrolysis of fats and
CH3(CH2)12COOH Tetradeconoic acid Myristic acid
oils of vegetable or
animal origin. CH3(CH2)14COOH Hexadecanoic acid Palmitic acid
CH3(CH2)16COOH Octadecanoic acid Stearic acid
COOH
Benzenecarboxylic acid Benzoic acid
CH 2COOH
Phenylethanoic acid Phenylacetic acid
6
OH 2-Hydroxypropanoic acid Lactic acid

CH 3CH-COOH
HOOC – COOH Ethanedioic acid Oxalic acid
HOOC(CH2)4COOH Hexanedioic acid Adipic acid
CH2=CH-COOH Propenoic acid Acrylic acid
OH 2,3-Dihydroxybutanedioic acid Tartaric acid

HOOC-CH-CH-COOH
OH
O
For monocarboxylic acids, [i.e. acids having one carboxy( C OH )
group], the IUPAC names are derived by replacing e ending of the
alkane by oic acid. As in the case of aldehydes, the carboxyl carbon
takes the “1” position in the parent chain, but this position number is not
indicated. However, in case of the dicarboxylic acids, the final -e of the
hydrocarbon is not dropped.
If there are multiple carboxyl groups on the same parent chain, the
suffix carboxylic acid can be used (as – dicarboxylic acid, - tricarboxylic
acid, etc.). In these cases, the carbon in the carboxyl group does not
count as being part of the main alkane chain. For example, citric acid is
named 2-hydroxypropane-1,2,3-tricarboxylic acid, rather than
2-carboxy-2-hydroxy-pentanedioic acid.
CH 2 COOH
HO C COOH
CH 2 COOH
The acidity of
citric acid carboxylic acids is
affected by various
Reactivity of Carboxylic Acids factors such as
inductive effect and
1. As Acids hydrogen bonding
etc.
As the name indicates, carboxylic acids are acidic in nature. The carboxylic
acids dissociate to yield the carboxylate ion and a proton. The proton
combines with the solvent (water) and exists as the hydronium ion.
O O
.. .. +
..
R C OH
.. + H R C O
.. + H3O
carboxylate ion
The carboxylate ion can be represented as a resonance hybrid of the following

two resonance structures.
7
Laboratory .. .. -
O O
..
detection of .. ..
carboxylic acids
R C R C
.. - ..
Carboxylic acids are O O
..
recognised by their .. ..
acidic nature. They
dissolve in aqueous As the two resonance structures are equivalent, they contribute equally to the
sodium hydroxide and
sodium bicarbonate. actual structure of the carboxylate ion which is given below.
The reaction with ..

sodium bicarbonate is O
..
accompanied by the
evolution of bubbles R C
of carbon dioxide.
O
..
..
Determination of the
physical constants
and formation of Thus, in the carboxylate ion, the charge is not localised on any one of the
derivatives leads to oxygen atoms but is distributed equally on both the oxygen atoms. This
their final
delocalisation of the charge stabilises the carboxylate ion.
identification. The
commonly prepared
derivatives of Since the charge is delocalised, the availability of electrons is reduced which
carboxylic acid results in the decreased basicity of the anion. Therefore, the equilibrium lies in
include amides, the forward direction which results in the dissociation of the carboxylic acid.
anilides and esters.
Another aspect related to the acidity of carboxylic acids is salt formation.
Carboxylic acids on treatment with bases such as NaOH yields salts.
The solubility in O O
sodium bicarbonate .. .. +
R C OH +NaOH R C ..
ONa
.. + H2 O
helps to distinguish ..
carboxylic acids from sodium salt
most phenols. Except of carboxylic acid
for dinitrophenols and
trinitrophenols, RCOOH + NaHCO3 RCOONa+ + H2O + CO2
phenols do not sodium
dissolve in sodium carboxylate
bicarbonate.
These salts are named by specifying the metal and replacing the –ic acid in
the name of the acid by –ate ending.
Even 5% sodium bicarbonate (NaHCO3) solution is basic enough (pH = 8.5) to

yield the sodium salt of a carboxylic acid. Thus, carboxylic acids react readily
with aqueous solutions of sodium hydroxide and sodium bicarbonate to form
soluble sodium salts.
Thus, water insoluble carboxylic acids can be differentiated from other water
insoluble nonacidic substances. Water insoluble carboxylic acids will dissolve
in aqueous sodium hydroxide or sodium bicarbonate but the nonacidic
compounds will not. After separating the basic aqueous solution, it can be
acidified with mineral acid to yield the carboxylic acid.
2. As Bases
The carboxylic acids also behave as bases and can be protonated as shown
8 below:
.. +
..
O
.. O
.. H
.. ..
R C ..
OH + H+ R C OH
..
(resonance stabilised)
The carbonyl group of the carboxylic acids is weakly basic and its protonation
yields the protonated carboxylic acid which has the following three resonance
contributors.
+
.. H .. H .. H
O O O
..
O
..
..
..
+ H+
C K ~ 106 C +C C
.. .. ..
R OH
.. R OH
.. R OH
.. R OH
..
+
Such a protonation or basicity plays an important role in many reactions of the

carboxylic acids and their derivatives about which you will study in the
following units of this block.
9.3 PHYSICAL PROPERTIES OF MONO-

CARBOXYLIC ACIDS
Physical properties such as melting point, boiling point and water solubility of
some straight chain carboxylic acids are listed in Table 9.2.
Table 9.2: Physical Properties of Carboxylic Acids
2
Acid Melting Boling point / K Solubility in H2O  10 at
3
point / K 293 K/kg dm
Methanoic acid 281 374 
Ethanoic acid 289 391 
Propanoic acid 252 414 
Butanoic acid 268 437 
Pentanoic acid 239 459 4.97
Hexanoic acid 270 478 0.968
Heptanoic acid 265 496 0.244
Octanoic acid 290 512 0.068
Nonanoic acid 288 528 0.026
Decanoic acid 305 543 0.015
Benzenecarboxylic 395 522 0.21

acid
9
You can see from Table 9.2 that the lower members are liquids at room
temperature. Table 9.2 also shows that the carboxylic acids having an even
number of carbon atoms have higher melting points as compared to the
carboxylic acids having an odd number of carbon atoms. Thus, it illustrates the
“saw-tooth” pattern, see Fig. 9.1. Can you think of the reason for this pattern?
The higher members and aromatic acids are solid at room temperature.
Fig. 9.1: Saw-tooth pattern of melting points.
Carboxylic acids are polar in nature. They can form hydrogen bonds in the
solid as well as in the liquid state. As a result, they generally have high boiling
points. In the solid state and under some conditions in gas and solution phase,
carboxylic acids exist as hydrogen-bonded dimers.
hydrogen bonding
O H O
CH3 C C CH3
O H O
dimer of ethanoic acid in vapour phase
Due to the hydrogen bonding, lower members of this family show appreciable
solubility in water. The first four monocarboxylic acids are miscible with water
in all proportions. But, as the chain length increases, the water solubility
decreases.
Let us now study how monocarboxylic acids are prepared.
9.4 PREPARATION OF MONOCARBOXYLIC

ACIDS
Let us first have a look at Table 9.3 wherein various methods which can be
used to prepare monocarboxylic acids have been listed. We will then discuss
10 each one of them in more detail.
Table 9.3: Some Methods of Preparation for Carboxylic Acids
1. Oxidation of Alkenes
1. KMnO4, OH, 
RCH CHR' RCOOH + R'COOH
2. H+, H2O
1. KMnO4, OH, 
RCH CHR'2 RCOOH + R'2 C O
2. H+, H2O
2. Side-Chain Oxidation of Alkylbenezenes

CH2R CHR 2 COOH Other oxidising
1. KMnO4, OH, 
agents used
or
2. H+, H2 O are Na2Cr2O7
and CrO3, etc.
alkylbenzene arenecarboxylic acid
3. Oxidation of Primary Alcohols

KMnO4 or
R CH2OH RCOOH
K2Cr2O7, H2SO4
primary carboxylic
alcohol acid
4. Oxidation of Aldehydes
1. Ag2O or Ag(NH3)+
2 OH

Other oxidising
RCHO RCOOH agents like KMnO4
2. H+, Heat
and chromic acid
can be used.
5. Oxidation of Methyl Ketones (Haloform reaction)

X2 1. OH
RCCH3 [RCOCX3] RCOOH + CHX3
OH 2. H+, H2O
O
6. Carbonation of Organometallic Reagents

CO2 H2O, H
RMgX RCO2MgX RCOOOH + Mg(OH)X
CO2 
H2O, H
RLi RCO2Li RCOOOH
7. Hydrolysis of Nitriles
H2O H2O
R C N   RCONH2  
RCOOH
H or OH H or OH
nitrile amide
1. Oxidation of Alkenes
Basic potassium permanganate cleaves alkenes to two carbonyl compounds.
If one of the substituents at the double bond is hydrogen, the cleavage product
is an aldehyde which is rapidly oxidised to a carboxylic acid under the reaction
conditions, i.e.,
R R'' R R''
1. KMnO4, OH, 
C C + C O + O C
2. H , H2O
R' H R' OH
alkene ketone carboxylic acid
11
In this oxidation, each carbon of the double bond becomes the carbon atom of
Potassium
permanganate is a the carbonyl group and a hydrogen substituent on the double bond is replaced
dark purple crystalline by a hydroxyl group.
solid which dissolves
in water to give Since the carboxylic acids are formed in these reactions as their potassium
intense purple carboxylate salts, the acidification step is necessary in order to isolate the
coloured solution. In
product as free acid.
permanganate anion,
MnO4, manganese
The intermediate in this reaction may be a diol which is oxidised further with
has an oxidation state
of +7. When used as the cleavage of carbon–carbon bond. The terminal =CH2 of 1-alkene is
an oxidising agent in completely oxidised to carbon dioxide and water. For example,
basic solution,
manganese reduces 1. KMnO4, OH, 
to MnO2 which is CH3(CH2)10CH CH2 + CH3(CH2)10COOH + CO2 + H2O
obtained as brown 2. H , H2O
precipitate. The 1-tridecene dodecanoic acid (84%)
oxidation state of Mn Note that the acid produced from the terminal alkene contains one carbon less
in MnO2 is +4.
You may recall that than the alkenes.
alkenes can be
oxidised to diols 2. Side Chain Oxidation of Alkylbenzenes
using cold dilute
KMnO4 (see sub-Sec. Aromatic carboxylic acids can be obtained by the oxidation of alkylbenzene.
17.2.7, Unit 17, The oxidation can be carried out by using potassium permanganate, Cr6+
Block 4, BCHCT-131 derivatives such as sodium dichromate or aqueous chromic acid.
Course).
The terminal carbon CH3 COOH
of 1-alkenes contains
two hydrogens on it, 1. KMnO4, OH, 
so it is oxidised to +
2. H , H2O
carbonic acid which is
present as its methylbenzene benzenecarboxylic acid
potassium carbonate. (toluene) (benzoic acid)
This on acidification (100%)
yields carbonic acid
which decomposes
into carbon dioxide
and water. 1. KMnO4, OH, 
O O CH2CH2CH2CH3 + COOH
+
2. H , H2O
H
KOCOK HOCOH
potassium carbonic
cabonate acid butylbenzene benzenecarboxylic acid
CO2 + H2O
carbon water
dioxide
CrO3, 40% H2SO4
C2H5 COOH
48 hrs., 373 K
Note that the alkyl benzenecarboxylic acid

ethylbenzene
chain, regardless of
the length, is oxidised
CH3 COOH
to a COOH group.
However, tert-alkyl NO 2 NO 2
15% HNO3, H2O
substituents do not
undergo oxidation 463 K, 5 hrs.
under these
conditions. F F
4-fluoro-2-nitrotoluene 4-fluoro-2-nitro-
benzenecarboxylic acid
(69%)
12
3. Oxidation of Primary Alcohols

Side-chain oxidation
You have already studied in Block 4, Unit 15, Sec. 15.7 of BCHCT-133 of alkylbenzenes is
course that primary alcohols can be oxidised to carboxylic acids using KMnO4, important in certain
metabolic processes.
CrO3, nitric acid etc. The carboxylic acid obtained contains the same number One way in which the
of carbon atoms as present in the starting alcohol. The initial product of body gets rid of
oxidation is an aldehyde. However, when aqueous KMnO4 is used, the foreign substances is
by oxidation in the
aldehyde is rapidly oxidised and the carboxylic acid is obtained as the product.
liver to compounds
which are more easily
O O excreted in the urine.
oxidation oxidation Methylbenzene, for
RCH2OH RCH RCOH example, is oxidised
to benzenecarboxylic
primary alcohol aldehyde carboxylic acid
acid which is easily
eliminated.
O CH3
KMnO4
CH3CH2CH(CH2)4CH2OH CH3CH2CH(CH2)4COH
H2SO4, H2O
CH3 CH3
methylbenzene
6-methyl-1-octanol 6-methyloctanoic acid O2
(66%) cytochrome
P450 (an
enzyme in the
liver)
When oxidation is carried out under basic conditions, the carboxylic acid is
COOH
obtained as the carboxylate salt which on acidification yields carboxylic acid.
O
1. KMnO4, OH
CH3CH2CH2CH2CHCOH benzenecarboxylic acid
CH3CH2CH2CH2CHCH2OH +
2. H , H2O
CH2CH3 CH2CH3
2-ethyl-1-hexanol 2-ethylhexanoic acid Sliver oxide is usually
(74%) prepared by mixing a
solution of silver
nitrate with sodium
4. Oxidation of Aldehydes hydroxide. The
precipitate obtained is
Aldehydes are readily oxidised to carboxylic acids by strong oxidising agents filtered, washed with
such as KMnO4, CrO3 and HNO3 as discussed above. A mild oxidising agent water and used as an
used for this oxidation is moist silver oxide suspended in an aqueous base. aqueous suspension.
O O
Tollens’ test is a
Ag2O, NaOH
Ag + CH3(CH2)5CO Na  + qualitative test for
CH3(CH2)5CH
H2O, 368 aldehydes. The
heptanal H
+ compound is treated
O with ammoniacal
silver nitrate in a
CH3(CH2)5COH clean test tube.
Formation of a shiny
heptanoic acid mirror of silver on the
(97%) walls of the test tube
is taken as a positive
In this reaction, Ag(I) is reduced to metallic silver. When the reaction is carried indication of the
presence of an
out in a clean test-tube, a mirror is deposited on the walls of the tube. This aldehyde or other
reaction forms the basis of the Tollens’ test. easily oxidisable
group.
Silver oxide selectively oxidises the aldehyde functional group and the other
sensitive groups such as double bonds and triple bonds are not affected. 13
Although this method gives the desired acid in good yields, its use is limited to
small scale reactions because silver oxide is expensive.
5. Oxidation of Methylketones
The haloform reaction which you studied in sub-Sec. 18.4.2, Unit 18, Block 4
of BCHCT-133 course, is occasionally used to prepare carboxylic acids from
readily available methylketones.
O O
1. Br2, NaOH, H2O
(CH3)3CCCH3 +
(CH3)3CCOH + CHBr3
2. H , H2O
3,3-dimethyl- 2,2-dimethylpropanoic bromoform
2-butanone acid
(71-74%)
Victor Grignard
(6th May 1871 – 6. Carbonation of Organometallic Reagents
13th Dec. 1935)
Organometallic compounds such as Grignard reagents and organolithium
Grignard reagents, compounds can be used for the synthesis of carboxylic acids.
RMgX, are named
after the French Organometallic reagents react with carbon dioxide to give salts of carboxylic
Chemist Victor acids. The salt is treated with a strong mineral acid to yield the carboxylic acid.
Grignard who
discovered them in O O
..
..
1900 and for which .. .. ..  +

+
H , H2O
MgBr R C OH + HO MgBr
..
he was awarded O
.. C O
.. R C O
..
Nobel Prize in 1912. MgBr bromomagnesium salt a carboxylic
R acid
of a carboxylic acid
Grignard reagents CH3 CH3

are usually prepared Mg CO2
by the reaction of an CH3CH2CHCl CH3CH2CHMgCl
diethyl ether
alkyl or aryl halide
2-chlorobutane 2-butylmagnesium
with magnesium chloride
metal in an ether or
hydrocarbon solvent. O O
+
H , H2O
CH3CH2CHCOMg2+Cl CH3CH2CHCOH
The reaction is of SN2
type and is most CH3 CH3
effective with primary 2-methylbutanoic acid
alkyl halides. It is (~77%)
slow with secondary
alkyl halides. With
tertiary alkyl halides,
elimination occurs.
1. Mg, diethyl ether
Aryl and vinyl halides
do not react. 2. CO2
CH3 + CH3
DMSO, Dimethyl 3. H , H2O
Br COOH
sulphoxide, is the
preferred solvent for 9-bromo-10-methylphenanthrene 10-methylphenanthrene-9-carboxylic acid
this reaction, but (82%)
alcohols and water-
alcohol mixtures have
Note that the acid obtained contains one carbon atom more than the alkyl or
also been used.
aryl halide used to prepare the Grignard reagent.
14
 +
Li CO 2 Li COOH
+
H , H2O
+ CO2
phenyllithium benzenecarboxylic acid
7. Hydrolysis of Nitriles
Primary and secondary alkyl halides may be converted to carboxylic acids

containing one more carbon atom using a two step process.
The first step involves the preparation of nitriles or alkyl cyanides. The nitrile
on hydrolysis in acidic or basic conditions yields the carboxylic acid.
DMSO
CH3CH2CH2CH2Br + NaCN CH3CH2CH2CH2CN
1-bromobutane pentanenitrile
KOH, H2O, 
+
H , H2O
-
CH3CH2CH2CH2COOH CH3CH2CH2CH2COO K+
pentanoic acid
(90%)
This method is complementary to carbonation of organometallic reagents as

the hydroxyl and carboxy groups present in the molecule do not need
protection in this method.
SAQ 1
How will you prepare the following carboxylic acids using Grignard reagents?
i) 2,2-Dimethylpentanoic acid
ii) Hexanoic acid
iii) 4-Methylbenezenecarboxylic acid

CH 3
COOH
9.5 REACTIONS OF CARBOXYLIC ACIDS

The reactions of carboxylic acids are given below in Table 9.4 followed by their
detailed discussion. 15
Table 9.4: Reactions of Carboxylic Acids
1. Esterification
O
+
H
RCOOH + R' OH RCOR' + H2O (Fischer Esterification)
RCOOH + CH2N2 RCOCH3 + N2 (by diazomethane)
2. Conversion to amides
+ heat
RCOOH + NH3 RCOOHNH4 RCONH2 + H2O
+ heat
RCOOH + R' NH2 RCOOHNH3R' RCONHR' + H2O
heat +
RCOOH + R'2 NH2 RCOOHNH2R'2 + H2O
3. Conversion to 2-halo acids

Red P
R CH2COOH + X2 R CHCOOH
X2 = Cl2 X
or Br2
4. Reduction
1. LiAlH4
RCOOH RCH2OH
2. H+, H2O
5. Decarboxylation
O
electrolysis
i) 2R C O R R + 2 CO2
O
CCl4
ii) RCOAg + Br2 RBr + CO2 + AgBr

6. Conversion to alkanoyl halides
RCOOH + SOCl2 RCOCl + SO2 + HCl
RCOOH + PCl3 3 RCOCl + H3PO3
RCOOH + PCl5 3 RCOCl + POCl3 + HCl
9.5.1 Esterification
Carboxylic acids react with alcohols in the presence of an acid catalyst to yield
esters. The reaction is known as Fischer esterification.
O
+
H
RCOOH + R' OH RCOR' + H2 O
carboxylic acid alcohol ester water
16
This reaction is an equilibrium process and can be driven in favour of the ester
by removing the water formed. The second way of increasing the yield of an
ester is by using one of the reactants in excess (Le Chatelier’s principle).
Generally, the cheaper of the two reactants is taken in excess. Thus,
esterifications are often carried out by using the alcohol as the solvent.
A wide variety of esters can be prepared using this method. The common acid
catalysts used are conc. sulphuric acid, hydrogen chloride or
p-toluenesulphonic acid. Some examples of ester formation are given below.
O O
H2SO4, 
CH3COH + CH3OH CH3COCH3 + H2O
ethanoic acid methanol methyl ethanoate
(excess) (85%)
O
H2SO4, 
BrCH2COOH + CH3CH2OH BrCH2COCH2CH3 + H2O
bromoethanoic ethanol ethyl (remove)
acid (excess) bromoethanoate
(70%)
When the carboxyl and hydroxyl groups are present in the same molecule, a
lactone (cyclic ester) is obtained by intramolecular esterification. For example,
O O
+
H
HOCH2CH2COH
O
4-hydroxybutanoic acid 2-oxacyclopentanone
(-butyrolactone)
Before studying the mechanism of acid-catalysed esterification, it is interesting

to know whether the oxygen of the water formed in the reaction comes from
the alcohol or from the acid. In an experiment using isotopically labelled
alcohol (having 18O isotope) it was observed that oxygen in the water
produced comes exclusively from the carboxylic acid. Thus, it was observed A carboxylic acid
that, does not react with
an alcohol unless a
O O strong acid is used as
+ a catalyst.
H
RCOH + H18OCH3 RC18OCH3 + H2O Protonation of the
carboxy group makes
and not, the carbonyl (>C=O)
group more
O electrophilic and
O
+ enables it to react
H
RCOH + H18OCH3 RCOCH3 + H218O with the alcohol which
is a weak
nucleophile.
In other words, the alcohol oxygen is incorporated into the ester. This and
other observations led to the following mechanism of esterification: 17
Step 1: Protonation of the carboxy group

+
H .. H .. H
..
O O
..
..
O
..
O
..
C + C C+ C
.. +H .. .. .. +
R O
.. H R O H R O
.. H R
O
H
H
+ ..
dihydroxycarbocation
Addition of alcohol to
carboxylic acid to The protonated carboxylic acid is susceptible to attack by nucleophiles such
form the tetrahedral
as alcohol, as shown in step 2.
intermediate is
analogous to the Step 2: Attack by alcohol
addition of an alcohol
to an aldehyde or H H
+
.. .. ..
ketone to form a O
..
O H O
..
hemiacetal which you +
.. .. H ..
have studied earlier C + CH3OH
.. R C O
.. + R C O
..
in sub Sec. 14.4.1 of .. +H
R O
.. H + H H
Unit-14 of Block 3 of O
..
O ..
..
BCHCT-133 course. H3 C H H3 C
tetrahedral
intermediate
Step 2 is the rate
determining
step in esterification Attack of the alcohol on the protonated carboxylic acid yields an initial adduct
reactions. which on loss of a proton yields the tetrahedral intermediate. The tetrahedral
intermediate eliminates water and yields the ester as shown in step 3.
Step 3: Elimination of water and deprotonation
.. H .. H
O O
..
..
H
+ H
.. +  H2O
R C O
.. + R C O
..
+H + H2O
H H
O O
..
..
.. ..
H3 C H3 C H
H H
+ .. ..
O O O
..
..
..
+
H
C C + C
.. + .. +H ..
R O
.. CH3 H3 C O
.. CH3 R O
.. CH3
Tertiary alcohols and phenols cannot be used in acid catalysed esterification.

Due to steric factors, tertiary alcohols react very slowly in the esterification
reaction and they usually undergo elimination instead of esterification. For
phenols also, the equilibrium constants of esterification are very low.
There are other ways of obtaining esters from tertiary alcohols and phenols
about which you have already studied in sub-Sec. 15.4.2, Unit 15, Block 4 of
18 BCHCT-133 course.
Another method of obtaining methyl esters from carboxylic acids involves the
use of diazomenthane, CH2N2. When a carboxylic acid is treated with
diazomethane in ether solution, it is rapidly converted into a methyl ester. Diazomethane is a
O toxic yellow gas. It is
both explosive and
RCOH + CH2N2 RCOOCH3 + N2 allergenic. Therefore,
this method can be
The following mechanism can be written for this esterification. used only for small
O scale preparations.
O
+ ..  + But by this method,
 N:
N: R C .. + CH3
O N
..
i) R C O H + :CH2 N the esterification is so
mild and free of side
O O reactions that in many
..  + cases it is the method
ii) R C O + CH3 N N: R C OCH3 + :N N:
..
.. of choice for the

synthesis of methyl
The first step involves the protonation of diazomethane. Therefore, you can esters.
understand that acidity of carboxylic acid is important in this reaction. The
resulting methyl diazonium ion has one of the best leaving groups, i.e.,
molecular nitrogen. Thus, an SN2 reaction of the carboxylate ion with the Step (i) is an acid-
methyldiazonium ion results in the displacement of N2 and formation of an base reaction.
ester. Note that here the oxygen of the carboxylate group acts as a
nucleophile whereas in acid-catalysed esterification, the carbonyl group
of the protonated carboxylic group behaves as an electrophile. This
illustrates two of the general ways in which carboxylic acids react.
The nucleophilic nature of the carboxylate ion is also illustrated by the reaction
of certain alkyl halides, particularly primary haloalkanes, with carboxylate ions.
For example,
O O
+ CH3COOH +
CH3CH2CH2CH2I + CH3CONa CH3CH2CH2CH2OCOCH3 + Na I
373 K
iodobutane sodium ethanoate butyl ethanoate
(95%)
9.5.2 Conversion to Amides

Carboxylic acids on reaction with ammonia or amines (primary or secondary)
can lead to amides via the initial formation of ammonium salts.
O O
..
..
..
..
.. ..  +
RCO
.. H + :NH3 ..
RCO HNH3
..
ammonia an ammonium alkanoate
On heating salt formation is reversed and nucleophilic attack by nitrogen on

the carbonyl carbon takes place. The elimination of water then leads to the
formations of an amide as shown below:
..  .. 
O
..
..
O O
..
..
O
..
..
..
..
.. proton +
.. ..
OH2 H 2O + C
..
C + :NH3 R C O
..H R C
.. transfer
R .. H
O R NH
.. 2
+
NH3 NH
.. 2
19
Some examples are given below:
298 K +
CH3CH2CH2COOH + NH3 CH3CH2CH2COONH4
butanoic acid ammonium butanoate
O

+ 458 K
CH3CH2CH2COOH NH4 CH3CH2CH2CNH2 + H2O
ammonium butanoate butanamide
O
458 K
CH3CH2CH2COOH + (CH3)2NH CH3CH2CH2CN(CH3)2 + H2O
butanoic acid N,N-dimethylamine N,N-dimethylbutanamide
(84%)
9.5.3 Hell-Vohlard-Zelinsky Reactoin

Aliphatic carboxylic acids react with bromine or chlorine in the presence of
phosphorous (or a phosphorus halide) to give 2-halo acids. This reaction is
known as Hell-Vollhard-Zelinski reaction after its discoverers.
Br
Br2, Catalytic red P
Phosphorus reacts CH3CH2CH2CH2COOH CH3CH2CH2CHCOOH + HBr
with Br2 to give PBr3. (PBr3)
pentanoic acid 2-bromopentanoic acid
If more than one equivalent of halogen is used in the reaction, then a

2,2-dihalo acid or 2,2,2-trihaloacetic acid is obtained. The mechanism of this
reaction is given below:
Step 1: Alkanoyl bromide formation
O O
3 RCH2COH + PBr3 3 RCH2CBr + H3PO3

alkanoyl bromide
Step 2: Enolisation
O
+ OH
H
RCH2CBr RCH C
enol
Br
Step 3: Bromination
OH O
Br2
RCH C RCHCBr + HBr
Br Br
Step 4: Exchange
O O O O
This can reenter
RCHCBr + RCH2COH RCHCOH + RCH2C Br the sequence at
step 2.
Br Br
The Hell-Volhard-Zelinsky reaction is of synthetic importance as the 2-halo

20
acids obtained can further react with a variety of nucleophiles as shown below:
Conversion to 2-hydroxy acids:
1. H2O, K2CO3, 
2. H+, H2O
R CH COOH R CH COOH
KX
X OH
2-halo acid 2-hydroxy acid
Conversion to 2-amino acids:
R CH COOH + 2 NH3 R CHCOO + NH4X

+
X NH3
2-halo acid 2-amino acid
Conversion to 2-cyano carboxylic acid:
 + +
KCN, NaOH H
R CH COOH R CH COO Na R CH COOH
KX, H2O
X CN CN
2-halo acid sodium 2-cyanocarboxylate 2-cyanocarboxylic acid
1. H2O, HO
2. H+, H2O
R CH COOH
COOH
a dicarboxylic acid
The cyano carboxylic acid can be subsequently hydrolysed to the dicarboxylic

acid as shown above.
9.5.4 Reducation
Carboxylic acids can be reduced by powerful reducing agents such as lithium
aluminium hydride, LiAlH4, to the primary alcohols.
1. LiAlH4, THF
RCOOH RCH2OH
2. H+, H2O
O
1. LiAlH4, diethyl ether
CH3C OH CH3CH2OH
2. H+, H2O
(100%)
CH3O CH3O
ether H2SO4
COOH + LiAlH4 CH 2OH
H2O
CH3O CH3O
(93%)
21
9.5.5 Decarboxylation
The loss of a molecule of carbon dioxide from a carboxylic acid is known as
decarboxylation.
The simple aliphatic carboxylic acids do not decarboxylate easily and some
structural features are required for it. For example, carboxylic acids having
strongly electron-attracting groups at the 2-position, decarboxylate readily on
heating at 373 to 423 K.
Among other carboxylic acids which decarboxylate readily are i) 3-keto acids;
ii) propanedioic acid (malonic acid) and its derivatives; and iii) carbonic acid
derivatives.
Decarboxylation reactions involving carboxyl radicals include Kolbe
electrolysis and Hunsdiecker reaction.
In Kolbe electrolysis, an aqueous solution of the sodium or potassium salt of a
carboxylic acid is subjected to electrolysis. The carboxylate ion loses an
electron at the anode to yield a carboxyl radical.
O
..
..
..
..
 anode
.. .
.. ..
R C ..
O R
..
(e) C O
carboxylate ion carboxyl radical
The carboxyl radical then decarboxylates and the alkyl radicals so produced
combine to yield an alkane.
O
..
..
..
R C ..
O R + CO2
.
.
alkyl
radical
2 R. R R
alkane
In Hundsdiecker reaction, the silver salt of a carboxylic acid is heated with a

halogen, usually bromine in CCl4.
RCOOAg+ + Br2 RBr + CO2 + AgBr
The reaction yields a bromoalkane having one carbon less than the starting
acid.
9.5.6 Conversion to Alkanoyl Halides

Carboxylic acids react with phosphorous trichloride (PCl3), phosphorous
pentachloride (PCl5) or thionyl chloride (SOCl2) to yield an alkanoyl chloride.
O O O
ClSCl
CH3CH2CH2COH CH3CH2CH2CCl + SO2 + HCl
reflux
butanoic acid butanoyl chloride
(85%)
An alkanoyl bromide can be obtained by the reaction of a carboxylic acid with

22 PBr3.
O O
COH CBr
PBr3
3 3 + H3PO3
(90%)
SAQ 2
Write the product obtained when 2-methylpropanoic acid reacts with the
following:
i) diazomethane in ether; ii) butanol, H2SO4
9.5 INDUSTRIAL USES OF CARBOXYLIC ACDIS

The carboxylic acids are very important industrially as they are used in the
manufacture of soaps as explained below:
Soaps: The sodium and potassium salts of long chain carboxylic acids were
used a soaps until the 19th century. These molecules have an ionic
hydrophilic (water-loving) carboxylate group and a nonpolar lipophilic (fat-
loving) hydrocarbon chain. In aqueous solution, they form spherical
aggregates known as micelles, as shown in Fig. 9.2.
Fig. 9.2: Schematic representation of a micelle.
The cleansing action of soap involves attracting nonpolar molecules as

grease, oil etc. to the nonpolar centre of the micelle. The outer polar part of
the micelle is attracted to water and the solubilised grease is washed away.
This is shown in Fig. 9.3.
Fig. 9.3: Cleansing action of soap. 23

A major disadvantage of the carboxylate soaps is that they combine with

calcium and magnesium ions often present in the water to form insoluble
scums.
Biodegradable This problem was taken care of when synthetic detergents were marketed in
means degradation or 1933. The first detergents were alkylbenzenesulphonates. The advantages of
breaking up into these detergents is that they do not form insoluble scum with hard water. An
simple molecules by example of a synthetic detergent is given below.
living organisms such
as bacteria.
 +
CH3(CH2)11 SO3 Na
sodium dodecylbenzenesulphonate
SO3, H2SO4 NaOH  +

R R SO 3H R SO3Na
H2O
R = branched alkyl chain Synthesis of alkylbenzenesulphonates
But these detergents are not readily biodegradable. After intensive research
linear alkanesulphonate detergents were introduced which are biodegrdable.
The general structure of linear alkanesulphonates is given below:
+
CH3(CH2)nCH2SO3Na
alkanesulphonate detergent, n = 1218
SAQ 3
What is the difference between soaps and detergents?
9.7 SUMMARY
In this Unit, you have studied that
 the carboxy group is the functional group of carboxylic acids.
 the carboxylic acids with long unbranched carbon chains are called fatty
acids.
 the carboxylic acids can be prepared by the following methods:
i) Oxidation of alkenes
ii) Side chain oxidation of alkylbenzenes
iii) Oxidation of primary alcohols
iv) Oxidation of aldehydes
v) Oxidation of methylketones
vi) Carbonation of organometallic reagents
24 vii) Hydrolysis of nitriles

 because of their acidity, carboxylic acids dissolve not only in aqueous

sodium hydroxide but also in aqueous solutions of weaker bases such as
sodium bicarbonate.
 carboxylic acids can be esterified using Fischer esterification or

diazomethane.
 using appropriate reagents and conditions, carboxylic acids can be

converted to:
i) esters
ii) amides
iii) 2halo acids
iv) alcohols
v) alkanes
vi) alkanoyl halides
 salts of carboxylic acids and sulphonic acids are used as soaps and
detergents.
9.8 TERMINAL QUESTIONS

1. What is the reason for the saw-tooth pattern of melting points of
carboxylic acids?
2. Assign structures to the compounds given in the following reactions:
+
Mg CO2 H ,H2O
a) CH3 Br A B C
diethyl ether
CH3
+
KMnO4, NaOH H ,H2O
b) CH3CH2CH2CHCH2CH2OH D E
H2O, 
O
+
Ag2O, NaOH H ,H2O
c) CH 2CH 2CH F G
H2O, 
CrO3
d) CH 2OH I
H2SO4, H2O, 
3. From a reaction mixture containing 4bromomethylbenzene and

4bromobenzenecarboxylic acid, how will you isolate pure acid?
4. A carboxylic acid having molecular formula C8H6O3 on reduction with
LiAlH4 followed by acidification yielded the following product.
HOH 2C CH 2OH
What is the structure of the acid? 25

5. Using decarboxylation reactions, how will you obtain the following, using
appropriate starting materials.
a) decane
b) phenylmethyl (benzyl) bromide, CH 2Br
9.9 ANSWERS
Self Assessment Questions
1. i) CH3 CH3
Mg/ether
CH3 CH2 CH2 C X CH3 CH2 CH2 C MgX
CH3 CH3
1. CO2
+
2. H3O
CH3
CH3 CH2 CH2 C COOH
CH3
ii) Similar to a) using CH3(CH2)4X.

CH 3
iii) Similar to a) starting with
X
2. i) CH3 CH3
CH2 CH COOH + CH2N2 CH3CHCOOCH3
ii) CH3
CH3 CH COOH + CH3CH2CH2CH2OH
CH3 O
CH3 CH C OCH2CH2CH2CH3
3. i) Soaps form insoluble scums with hard water whereas detergents do

not,
ii) Soaps are sodium or potassium salts of long chain in carboxylic acids
whereas detergents are sodium salts of sulphonic acids.
Terminal Questions
1. The saw-tooth pattern can be explained due to the fact that in the solid
26 state, the London forces among the molecules having odd number of
carbon atoms are weaker than those in the molecules having even
number of carbon atoms. This is because the molecules of carboxylic
acids having odd number of carbon atoms do not fit well in the crystal
lattice as compared to those of the carboxylic acids having even number
of carbon atoms.
O
2. a)  2+ 
A CH3 MgBr, B  CH3 CO Mg Br,
O
C  CH3 C OH
CH3 CH3
b) D CH3CH2CH2CHCH2COONa+, E CH3CH2CH2CHCH2COOH
 +
c) F  CH 2CH 2COO Na , G  CH 2CH 2COOH
d) I  COOH
3. Dissolve the mixture in aqueous alkali, separate aqueous layer and

acidify to get 4bromobenzenecarboxylic acid.
4. Molecular formula, C8H6O3
OHC COOH
5. a) Kolbe Electrolysis of sodium or potassium salt of pentanoic acid.
b) heating CH2COOAg with Br 2; using Hunsdiecker reaction.
27
UNIT 10
CARBOXYLIC ACID
DERIVATIVES
Structure
10.1 Introduction 10.6 Carboxylic Acid Esters
Objectives Preparation of Carboxylic Acid

Esters
10.2 Structure and Reactivity of
Carboxylic Acid Reactions of Carboxylic Acid
Derivatives esters
10.3 Physical Properties of Reformatsky Reaction

Carboxylic Acid Derivatives
10.7 Amides
10.4 Carboxylic Acid Halides
Preparation of Amides
Preparation of Carboxylic Acid
Reactions of Amides
Halides
10.8 Summary
Reactions of Carboxylic Acid
Halides 10.9 Terminal Questions
10.5 Carboxylic Acid Anhydrides 10.10 Answers
Preparation of Carboxylic Acid

Anhydrides
Reactions of Carboxylic Acid

Anhydrides
10.1 INTRODUCTION
In the last unit, you have studied about the chemistry of carboxylic acids.
There, in Sec. 9.5 under the reactions of carboxylic acids, you came
across the formation of derivatives of carboxylic acids.
A functional derivative of carboxylic acid is a compound which results on

replacement of the hydroxyl group of the carboxylic acid by some other
group, L. A characteristic feature of these derivatives is that they
regenerate the carboxylic acid on hydrolysis, i.e.
28
Unit 10 Carboxylic Acid Derivatives
O O
RCL + H2 O RCOH + HL
Carboxylic acid Water Carboxylic Conjugate
derivative acid acid of L
Various functional derivatives of carboxylic acids are possible depending

upon the nature of L. The functional derivatives which you will study in this
unit include carboxylic acid halides also called alkanoyl halides,
anhydrides, esters and amides. The general structures of carboxylic acid
and these functional derivatives can be represented as follow:
O O O O
R C OH R C X R C O C R'
a carboxylic acid an alkanoyl an anhydride
halide
O O
R C R' R C NH2
an ester an amide
O
You can see that all of these derivatives contain a R C or alkanoyl
group in their structure. While studying this unit, you will realise that there
is not only a structural similarity among carboxylic acids and their
derivatives but also a close relationship in their chemistry.

 define carboxylic acid derivatives;
 give examples of various carboxylic acid derivatives;
 comment on the acidic and basic behavior of various carboxylic acid

derivatives;
 correlate the reactivities of carboxylic acid derivatives with their

structures;
 outline the synthesis of various carboxylic acid derivatives;
 explain the reactions of various carboxylic acid derivatives;
 compare the behavior of various carboxylic acid derivatives, reaction

conditions required in various nucleophilic addition-elimination reactions
like hydrolysis, formation of amides, etc., and the nature of products
obtained;
 describe the reactions of various carboxylic acid derivatives with

organometallic reagents; and
 explain the reduction reactions undergone by carboxylic acid

derivatives.
29
10.2 STRUCTURE AND REACTIVITY OF

CARBOXYLIC ACID DERIVATIVES
Similar to the structure of carbonyl compounds and carboxylic acids, the
derivatives of carboxylic acids have trigonal geometry, i.e., all the bonds to the
carbonyl carbon are in the same plane. This is shown in Fig. 10.1.
O
L
C
R
Fig. 10.1: Planar arrangement of bonds to the carbonyl carbon in carboxylic acid
derivatives.
An important structural feature of carboxylic acid derivatives is that the atom

O
attached to the R C group bears an unshared pair of electrons which is
capable of interacting with the π electrons of the carbonyl group. This is shown
in Fig. 10.2.
Individual p orbitals in carboxylic acid Extended  orbital system in carboxylic

derivatives acid derivatives
Fig. 10.2: The extended π electron system in carboxylic acid derivatives.
This electron delocalisation can be represented by the following resonance

structures.
:
O: :O:
R C R C
+
:
L L
I II
The extent of this electron delocalisation depends on the electron donating

properties of L. Thus, a less electronegative L will donate the electrons more
easily than a more electronegative L. The electron release from L reduces the
polarisation of the carbonyl group, thereby, decreasing its electrophilic
character. Thus, the greater the electron release from L, the greater is its
stabilising effect. Consequently, when L is more electronegative, the extent of
resonance decreases and the reactivity increases. Thus, the reactivity of
carboxylic acid derivatives towards nucleophilic substitution reactions follows
30 the following order:
O O O O O
A derivative higher in
RCCl > RCOCR > RCOR > this order can be
RCNH2
converted to the one
alkanoyl halide anhydride ester amide lower but not vice-
versa.
You will study the nucleophilic substitution reactions of carboxylic acid
derivatives in detail in the later sections of this unit.
The degree of resonance stabilisation is also reflected in the structural

parameters and spectral characteristics of carboxylic acid derivatives about
which you will study in the next section.
But before that let us understand the reactivity of carboxylic acid derivatives as
acids and bases.
Basicity and Acidity of Carboxylic Acid Derivatives
Carboxylic acid derivatives are weakly basic at the carbonyl oxygen which can
be protonated using strong acids. This property is particularly useful in some
of the acid-catalysed reactions of esters and amides.
.. H .. H .. H
+ O O
..
..
O O
..
..
+
H
C C C+ C
.. .. ..
R L R L R L R L+
pKa values of the

The pKa values for the conjugate acids of carboxylic acid derivatives show that conjugate acids of
alkanoyl halides are the weakest bases as their conjugate acids have the carboxylic acid
derivatives.
lowest pKa and are, therefore, strongest acids. Esters are about as basic as
+ H + H H
carboxylic acids whereas amides are the most basic. +
:
:
O O O
: :
: :
:
RCCl < RCOR ' < RCNH 2
:
The acidity of the -hydrogens next to the carbonyl group shows the following pKa ~  9 ~ 10 ~0
order amongst carboxylic acid derivatives.
O O O
CH3CCl < CH3COCH3 < CH CN(CH )
3 3 2
pKa ~ 16 pKa ~ 25 pKa ~ 30
Primary and secondary amides are deprotonated at nitrogen to give an

amidate ion which is resonance stabilised in the same way as the carboxylate
ion.

..
O
..
O
..
O
..
..
..
..
C H+ + C C
.. ..
 ..
R NH2 R NH R NH
pKa ~ 15 an amidate ion
31
10.3 PHYSICAL PROPERTIES OF CARBOXYLIC

ACID DERIVATIVES
It was pointed out in the earlier section that the extent of resonance is
reflected in the structural parameters. This can be understood when we
compare the C-L bond lengths in various carboxylic acid derivatives with the
C-L bond lengths in the compounds of the type R-L. These bond lengths are
listed in Table 10.1.
Table 10.1: C-L Bond lengths of some carboxylic acid derivatives and
compounds of R-L type
O
L R L (pm)
R C L (pm)
Cl 179 178
OCH3 136 143
NH2 136 147
The bond lengths shown in Table 10.1 indicate that as we go from the most
reactive alkanoyl halides to the much less reactive esters and amides, the C-L
bond becomes shorter as compared to the normal C-L single bond. Thus, in
amides, the contribution of the dipolar structure II as discussed earlier, is
strong enough to impart some double bond character to the carbon-nitrogen
bond. The double bond character is also indicated by a barrier of 75 to
84 kJ mol1 to the rotation of the carbon-nitrogen bond.
O R' R R'
C N C N
R R" O R"
The other physical properties for various carboxylic acid derivatives are briefly
stated below.
Alkanoyl Halides and Anhydrides
The lower members of these derivatives are dense, water-insoluble liquids

with piercing odours. Their boiling points are not very different from those of
other polar molecules of similar weight and shape. Some examples are given
below:
O O O CH3
O
C C C C
O CH3 CH3 CH CH3 CH3 C Cl
CH3
b.p. 413 K b.p. 403 K b.p. 324 K
O O O
CH3 C O CH2CH3 C Cl C OCH3
b.p. 330 K b.p. 470 K b.p. 486 K

32
Esters: The lower members of this class are volatile, fragrant liquids having
lower density than water. Most esters are not soluble in water.
Amides: The lower members are water-soluble, polar in nature and have high
boiling points. Primary and secondary amides associate to form hydrogen
bonded dimers or higher aggregates in solid and liquid state.
O
C
CH3 NH2
ethanamide
m.p. 355 K O
b.p. 494 K CH3
H C N
CH3
A number of amides have high dielectric constants.
N, N-Dimethylmethanamide (commonly known as N, N-dimethylfomamide, N,N-Dimethylmethanamide
abbreviated as DMF) is widely used as a polar aprotic solvent.
SAQ 1
Which carboxylic acid derivative is least
a) reactive towards nucleophilic substitution reactions?
b) basic?
10.4 CARBOXYLIC ACID HALIDES

Carboxylic acid halides are important class of compounds belonging to
carboxylic acid derivatives. In this section, we will be dealing with the
preparation and the reactions of this class of carboxylic acid derivatives.
10.4.1 Preparation of Carboxylic Acid Halides

Carboxylic acid halides can be prepared from carboxylic acids using the acid
chlorides of inorganic acids such as PCl5 (acid chloride of phosphoric acid),
PCl3 (acid chloride of phosphorous acid) and SOCl2 (acid chloride of
sulphurous acid). The general reactions can be represented as shown below:
O O
RCOH + PCl5 RCCl + POCl3 + HCl
phosophrous
pentachloride
O O
3 RCOH + PCl3 3 RCCl + H3PO3
phosophrous
trichloride
O O
RCOH + SOCl2 RCCl + SO2 + HCl
thionyl chloride
33
Carboxylic acid fluorides, bromides and iodides are prepared from carboxylic
acid chlorides by reaction with HF, HBr or HI, respectively.
O O
HX = HF, HBr or HI
RCCl + HX RCX + HCl
10.4.2 Reactions of Carboxylic Acid Halides

The reactions of carboxylic acid halides are listed in Table 10.4.
Table 10.4: Reactions of Carboxylic Acid Halides
A. Reactions with Nucleophiles
O O

RCL + Nu RCNu + L
where NuH = H2O, RCOOH, ROH, ArOH,NH3, NR2 and organometallic

reagents.
B. Reduction
O O
H2/catalyst
RCL or hydride
RCH
aldehyde
reduction
C. Friedel-Crafts reactions (discussed in Unit 11, Block-3 of BCHCT-135 Course).
The reactions of carboxylic acid halides and carboxylic acid derivatives with
nucleophiles proceed via addition–elimination steps which lead to the
nucleophilic substitution at the carbonyl carbon. This is shown below:

..
O
..
O O
..
..
..
..
..
RCL + :Nu R C L RCNu + L
Nu
Thus, the nucleophile: Nu has substituted the group L in the carboxylic acid
derivative.
This reaction has little
synthetic value Carboxylic acid halides react with a variety of nucleophilic reagents such as
because acid halides water, carboxylic acids, alcohols and phenols, amines and organometallic
are themselves reagents. Let us study each of these reactions in detail using the examples of
usually prepared from carboxylic acid chlorides as these are the most readily accessible among the
the acids. halides.
1. Reaction with Water
It was pointed out earlier that carboxylic acid derivatives, on hydrolysis,

yield carboxylic acids. Thus, carboxylic acid halides react with water to
34 give carboxylic acids. For example,
O O
CH3CH2CCl + HOH CH3CH2COH + HCl
propanoyl propanoic acid
chloride (100%)
2. Reaction with Carboxylic Acids
Carboxylic acid halides on reaction with carboxylic acid yield acid

anhydrides, i.e.
O O O O
Pyridine acts both as
RCCl + R'COH + RCOCR' + Cl a catalyst as well as a
+
N N base to neutralise the
.. H hydrogen chloride
alkanoyl carboxylic pyridine carboxylic acid pyridinium formed in the
chloride acid anhydride chloride reaction.
Salts of carboxylic acids also react with a carboxylic acid halides to yield
the acid anhydrides. For example,
O O O O
+
: :
C2H5CCl + Na :O C CH3 C2 H5 C O C CH3 + NaCl

propanoyl (excess) ethanoic propanoic
chloride sodium ethanoate anhydride
3. Reaction with Alcohols and Phenols
The reaction of carboxylic acid halides with alcohols and phenols yields
esters. A base is usually added to neutralise the hydrogen chloride formed
as by-product. Usually pyridine, amines or alkali metal hydroxides are used
as bases.
O O
N(CH2CH3)3 +
CH3CCl + HOCH2CH2CH3 CH3COCH2CH2CH3 + HN(CH2CH3)3Cl
ethanoyl propanol propyl ethanoate triethylammonium
chloride hydrochloride
O
OH O C CH3
O
ether
CH3CCl + pyridine
+ HCl
CH3 CH3 CH3 CH3
(75%)
4. Reaction with Ammonia and Amines
Ammonia, primary and secondary amines react with carboxylic acid

halides to yield amides. The reaction with ammonia yields a primary amide
as shown below:
O O
+
CH3(CH2)8C Cl + 2 NH3 CH3(CH2)8C NH2 + NH4Cl
(73%)
35
The reaction with primary amines yields a secondary amide whereas the
reaction with secondary amines gives tertiary amide.
O O
.. ..
Ph C Cl + PhCH2CH2NH2 + Ph C NHCH2CH2Ph +
+
N
.. N
pyridine H Cl
O O
Ph C Cl + N H + NaOH Ph C + H2O + Na+Cl
..
N
..
(77-81%)
What about the tertiary amines? Do they react with carboxylic acid
halides? Before finding an answer to these questions, let us first try to
understand the mechanism of the amide formation which is given below:
..
O
..
O O
..
H O
..
..
..
..
..
..
..
.. .. H2NR .. +
R C Cl R C Cl.. R C NH R R C NH R + H3NR Cl
..
..
.. +
+
..

NH2 R NH2 R + Cl
..
..
..
..
The last step in the mechanism involves loss of a proton from nitrogen
which is not possible when the reaction is carried out with tertiary amines.
O O
+ H+
R C Cl + (CH3)3N: RCN(CH3)3Cl No amide
a tertiary alkanoyl
amine ammonium
chloride
An important aspect of amide formation is that, for each equivalent of the

amide formed, an additional equivalent of base is required to neutralise the
hydrogen chloride formed. When the amine used in the reaction is cheap
and readily available, it is used in excess to serve as a base also. When
the amine used to form the amide is expensive and, hence, cannot be
used in excess, a tertiary amine, which does not interfere with the reaction,
can be used as a base.
5. Reaction with Organometallic Reagents
Carboxylic acid halides react with a number of organometallic compounds

to yield ketones. When a Grignard reagent is used, the best results are
obtained if the reaction is carried out at low temperature using one
equivalent of the Grignard reagent.
O O
R C X + R' MgBr R C R' + X Mg Br
36
If an excess of the Grignard reagent is used, the ketone obtained reacts

further to yield an alcohol as shown below:
+
O O OMgX OH
R' MgX R' MgX H2O
R C Cl R C R' R C R' R C R'
R' R'
a tertiary
alcohol
Thus, to synthesise a ketone from a carboxylic acid halide, the

organometallic reagent used should be so chosen that it reacts much
faster with the starting halide than it does with the product ketone. Two
types of organometallic reagents which satisfy this requirement are lithium
organocuprate reagents and organocadmium reagents.
Lithium organocuprate reagents such as lithium dialkyl-and diaryl cuprates

are prepared through the reaction of an alkyl or aryllthium reagent with a
cuprous salt.
ether
2 RLi + CuX LiCuR2 + LiX
alkyllithium cuprous lithium lithium
halide dialkylcuprate halide
The reaction of a carboxylic acid halide with lithium diorganocuprate yields

a ketone.
O O
ether
LiCuR2 + R' CCl R' CR + RCu + LiCl
195 K
lithium alkanoyl ketone alkyl lithium
dialkylcuprate halide copper chloride
Organocadmium reagents such as dialkylcadmium and diarylcadmium are

prepared by treating Grignard reagents with cadmium chloride.
CdCl2
2 CH3CH2MgBr (CH3CH2)2Cd
ether
ethylmagnesium diethylcadmium
bromide
CdCl2
2 C6H5MgBr (C6H5)2Cd
ether
phenylmagnesium diphenylcadmium
bromide
The desired ketone can be prepared by the reaction of the suitable

organocadmium reagent with a suitable carboxylic acid halide.
O O
R2Cd + R' CX R' CR
organocadmium carboxylic ketone
reagent acid halide 37
Secondary and tertiary lithium alkylcuprates and also the secondary and
tertiary alkylcadmium reagents are not stable and decompose readily and
hence, cannot be employed for ketone synthesis. This then limits the
synthetic utility of these reactions employed for ketone synthesis. To
primary alkyl and arylcuprates and to primary dialkyl or diarylcadmium
reagents.
B. Reduction
Carboxylic acid halides can be reduced to aldehydes by either of two

methods: the first method involves catalytic hydrogenation and the second
involves hydride reduction.
In catalytic reduction, the carboxylic acid halide is hydrogenated using a

special catalyst such as palladium deposited on barium sulphate poisoned
with an amine such as quinoline. The poisoning of the catalyst moderates its
effectiveness and hence inhibits the subsequent reduction of the product
aldehyde to alcohol. This reaction is called the Rosenmund reduction.
O O
CH 2CCl CH 2CH + HCl
H2, Pd-BaSO4, quinoline
(71%)
O O
CCl CH
H2, Pd/BaSO4
xylene, heat
naphthalene-2- carbonyl naphthalene-2-carbaldehyde

chloride (74-81%)
H3CO H3CO
O O
H2, Pd/BaSO4
H3CO CCl H3CO CH
xylene, 423 K
H3CO H3CO
3,4,5-trimethoxybenzoyl chloride 3,4,5-trimethoxybenzaldehyde

(71%)
The hydride reduction using ordinary reducing hydrides, such as sodium

borohydride or lithium aluminum hydride, coverts the aldehydes obtained
initially in the reaction to alcohols. This over reduction can be prevented by
using a modified lithium aluminium hydride namely, lithium tri(tert-butoxy)
aluminium hydride which is obtained by the reaction of lithium aluminium
hydride with three equivalents of 2-methyl-2-propanol (tert-butanol).
+
+
Li AlH4 + 3 (CH3)3C O H LiH Al[O C(CH3)3]3 + 3 H2
2-methyl- 2-propanol lithium tri(tert- butoxy)

aluminium hydride
38
In lithium tri(tert-butoxy) aluminium hydride, three of the reactive hydride

groups of lithium aluminium hydride are replaced with alkoxy groups and
hence, the one remaining hydride reduces only the most reactive functional
groups. Because acid halides are more reactive towards nucleophiles than
aldehydes, the reagent preferentially reduces the carboxylic acid halide rather
than the product aldehyde
O O
1. ether
RCCl + LiAl[OC(CH3)3]3H + RCH + LiCl + Al[OC(CH3)3]3
2. H , H2O
C. Friedel-Crafts Reactions
The Friedel-Crafts alkanoylation (acylation of aromatic compounds using

alkanoyl halides was dealt with in Unit 11, Block 3 of BCHCT-133 Course.
SAQ 2
How will you convert butanoyl chloride into the following products.
O
a) CH3CH2CH2COH
O O
b) CH3CH2CH2COCCH3
O
c) CH3CH2CH2CO
O
d) CH3CH2CH2CN(CH3)2
O
e) CH3CH2CH2CCH2CH3
O
f) CH3CH2CH2CH
10.5 CARBOXYLIC ACID ANHYDRIDES

Carboxylic acids anhydrides are another important group of carboxylic acids
derivatives. In this section, you will study about the preparation and important
reactions of carboxylic acid anhydrides.
10.5.1 Preparation of Carboxylic Acid Anhydrides

Carboxylic acid anhydrides can be prepared using the methods listed in
Table 10.5. 39
Table 10.5: Methods of Preparation of Carboxylic Acid Anhydride

1. From carboxylic acid halides and carboxylic acids
pyridine
RCOOH + R'COCl RCO O COR' + HCl
2. From Ketene and carboxylic acids
CH2 C O + RCOOH RCO O COCH3
(used in commercial preparation of ethanoic anhydride)

3. Using other anhydrides
P2O5
2 R COOH R CO O CO R
or ethanoic
anhydride
Let us now study these methods in detail.
1. From carboxylic acid halides
A general method of It was pointed out in the last section (sub-Sec.10.4.2) that carboxylic acid
preparation of halides react with carboxylic acids or carboxylate salts to give carboxylic acid
substituted ketenes is anhydrides. This reaction can be used prepare both the simple and the mixed
based on the
dehydrohalogenation anhydrides.
of alkanoyl halides or
the dehalogenation of 2. From ketene and carboxylic acids
2-halo-alkanoyl
halides. Carboxylic acid anhydrides can also be prepared by the reaction of ketene
with carboxylic acids.
O
RCH2CCl N(CH2CH3)3 O O O
+
RCH C O+HN (CH2CH3) 3Cl
 CH2 C O + RCOH R C O C CH 3
O ketene carboxylic anhydride
RCH2CCl Zn acid
Br
RCH C O + ZnClBr The commercial production of ethanoic anhydride, based on the above
reaction, involves the use of ethanoic acid as the carboxylic acid.
3. Using other anhydrides
Most anhydrides may themselves be used to form other anhydrides. Examples

given below illustrate the use of P2O5 (an inorganic anhydride) and ethanoic
anhydride.
O O O
2 CF 3 C OH + P2O 5 2 CF3 C O C CF3 + complex phosphates
trifluoroethanoic phosphorus trifluroethanoic
acid pentoxide anhydride
(74%)
O
O
O O O
CH2 C OH CH2 C
CH3 CH + CH3 C O C CH3 CH3 CH 2 CH
O +3 C OH
CH2 C OH CH2 C
O
O
(>90%)
40 a cyclic anhydride
Cyclic anhydrides containing five- and six-membered rings can also be readily
prepared just by heating the dicarboxylic acid. For example,
1,2-benzenedicarboxylic acid gives 1,2-benzenedicarboxylic anhydride on
heating.
O O
C OH C
fuse (melt)
O + H2O
sublimes
C OH C
O O
1,2-benzenedicarboxylic acid 1,2-benzenedicarboxylic
(phthalic acid) anhydride
(phthalic anhydride)
10.5.2 Reactions of Carboxylic Acid Anhydrides

Table 10.6 lists the reactions exhibited by carboxylic acid anhydrides.
Table 10.6: Reactions of Acid Anhydrides
A. Reactions with nucleophiles

1. Hydrolysis
O
O
R C
O + H2O 2R C OH
R C
O
2. Reaction with alcohols

O
O O
R C
O + R'OH R C OR' + R COH
R C
O
3. Reaction with ammonia and amines
O
O O
R C R'
O + H N R C N R' + R COH
R C R"
R"
O
B. Friedel-Crafts alkanoylations
O
O C R
O
R C
O + AlCl3 + R COH
R C
O
41
The reactions of carboxylic acid anhydrides with nucleophiles are analogous

to those of the carboxylic acid halides which you have studied in the last
section. The difference here is that the leaving group is a carboxylate ion
instead of the halide ion in the case of carboxylic acid halides. The reactions
of carboxylic acid anhydrides with water, alcohols and amines are given
below:
1. Hydrolysis
O O O
RCOCR + H2O 2 RCOH
carboxylic acid carboxylic acid
anhydride
2. Reaction with alcohols
O O O O
RCOCR + R'OH RCOR ' + RCOH
carboxylic acid alcohol ester carboxylic

anhydride acid
3. Reaction with ammonia and amines
O O O O
+
RCOCR + 2 NH 3 RCNH 2 + RCO NH 4
carboxylic acid ammonia amide ammonium
anhydride carboxylate salt
O O O O
 +
RCOCR + 2 R 2'NH RCNR 2' + RCO H2NR 2'
carboxylic acid amine amide ammonium
anhydride carboxylate salt
The products in this reaction are amide and carboxylic acid. The carboxylic
acid reacts with ammonia or amine to form a salt. Therefore, two moles of
ammonia or amines are required. Another alternative, as you have studied in
the case of carboxylic acid halides is to use one equivalent of a tertiary amine.
The general nucleophilic addition-elimination of anhydrides is shown below:
:O:
:
:O: :O : :O : :O: :O : :O: :O:

+
: :
: :

: :
RC O CR + :NuH RC O CR RC NuH + :OCR RCNu + HOCR

+
NuH
The nucleophilic reactions which you have just studied can be used to
synthesise one carboxylic acid derivative from another, as you will study in the
later sections.
If you recall the order of relativities of various carboxylic acid derivatives given
42 in Sec. 10.2, then you will realise that the less reactive carboxylic acid
derivatives can be synthesised from the more reactive ones but the reverse is
usually difficult and requires special conditions or a catalyst.
B. Friedel-Crafts Alkanoylations
Carboxylic acid anhydrides also serve as sources of alkanoyl cations and can
be used in Friedel-Crafts alkanoylations as shown below.
O
H O O CCH 3 O
AlCl3
+ CH 3COCCH 3 + CH 3COH
313 K
ethanoic ethanoic acid
anhydride
benzene 1-phenylethanone
(76-83%)
(acetophenone)
SAQ 3
Write the products of the following reactions:
O O
H2O
a) CH 3COCCH 3
ethanoic
anhydride
O O
CH3OH
b) CH3CH2COCCH2CH3
propanoic anhydride
O O CH3
C O C
CH 3 CH NH2
c)
cyclohexanecarboxylic
anhydride
Esters have pleasing

10.6 CARBOXYLIC ACID ESTERS odors.
Carboxylic acid esters constitute a very important class of carboxylic acid CH2OH
derivatives. Some examples of naturally occurring esters are given below.
CHOH
O CH3 O CH3 CH2OH
1,2,3-propanetriol
CH 3COCH 2CH 2CHCH 3 CH 3CH 2CH 2CH 2COCH 2CH 2CHCH 3 (glycerol)
3-methylbutyl ethanoate 3-methylbutyl pentanoate O
(component of banana flavour) (component of apple flavour) CH2OCR
O
O
HCOCR'
COCH 3 O
CH2OCR''
1,2,3-propanetriol
OH triester
(Triglyceride)
methyl 2-hydroxybenzenecarboxylate
(principal component of oil of wintergreen)
43
Triesters of 1,2,3 -propanetriol (glycerol) constitute the oils and fats found in
plants and animals.
As the esters contain alkyl and alkanoyl (acyl) groups, they are named as
alkyl alkanoates. The alkyl group is cited first, followed by the name of the
alkanoyl (acyl) portion which is named by replacing the ic ending of the
carboxylic acid by the suffix ate. Some more examples are given below:
O O O
CH3COCH3 CH3COCH2CH3 CH3CH2COCH3
methyl ethanoate ethyl ethanoate methyl propanoate
The systematic names of cyclic esters, i.e., lactones are illustrated by the
following examples.
O   


1 3
  2
1
2
1
O2 O H3C O
O O
2-oxacyclobutanone 2-oxacyclopentanone 2-oxa-3-methylcyclo-
(-propiolactone) (-butyrolactone) pentanone
(-valerolactone)
Let us now study the methods of preparation of carboxylic acid esters.
10.6.1 Preparation of Carboxylic Acid Esters

Let us first list the methods of ester formation which you have already studied.
1. From the reaction of carboxylic acids and alcohols (Fischer

esterification): It was dealt with in detail in Sec. 9.5, Unit 9.
2. From carboxylic acids using diazomethane: It was also dealt with in

Sec. 9.6, Unit 9.
3. From carboxylic acid halides: The reaction of carboxylic acid halides

with alcohols and phenols also yields esters. It involves the use of a
weak base. It was discussed in Sub-Sec. 10.4.2.
4. From carboxylic acid anhydrides: Carboxylic acid anhydrides react

with alcohols in the presence of acid catalysts to give esters. This
reaction was discussed in sub-Sec. 10.5.2.
In addition to the above methods, esters can also be prepared by ester

interchange which is discussed below.
5. Ester interchange: Esters can also be obtained by ester interchange.

When an ester reacts with an alcohol under acidic conditions or with an
alkoxide ion under basic conditions, a new ester is formed. This is called
transesterification. The general reaction can be represented as shown
below:
O O
RCOR' + R"OH RCOR" + R'OH
Transesterification will be discussed in detail under the reactions of

44 esters in the next sub-section.
10.6.2 Reactions of Carboxylic Acid Esters

The reactions of esters are listed in Table 10.7 followed by their detailed
discussion.
Table 10.7: Reactions of Esters
1. Hydrolysis
O O
+
H
R C O R' + H2O R C OH + R' OH
O O
 
R C O R' + OH R C O + R' OH
H2O
2. Conversion to amides
O O
R" R"
R C O OR' + HN R-C-N + R' OH
R"' R"'
R" and/or R''' may be H
3. Conversion to other esters: transesterification
O O
+
H
R C O R' + R'' OH R C O R" + R' OH
4. Reaction with Grignard reagents
O OMgX
ether
R C OR' + 2 R" MgX R C R" + R'OMgX
R"
+
H
OH
R C R"
R"
5. Reduction
O
R C O R' + H2 Ni
R CH 2OH + R' OH
O
R C O R' + LiAlH4 R CH 2OH + R' OH
O
C2H5OH
R C OR' + Na R CH 2OH + R' OH
6. Formation of enolates
O 
O

RCH 2COR ' + :B RCH C + BH
OR'
ester ester enolate
45
1. Hydrolysis
In contrast to the hydrolysis of carboxylic acid halides and anhydrides, esters

Base catalysed do not react with water unless a catalyst is present. Both acid catalysed and
hydrolysis of esters is
base catalysed hydrolysis reactions are possible.
called saponification
because it was
The acid catalysed hydrolysis is just the reverse of acid catalysed formation of
initially used in the
manufacture of soaps
esters which was discussed in detail in Sec. 9.5, Unit 9 .You studied in
from fats. This term is Sec. 9.5 that esterification is an equilibrium reaction, i.e.,
now sometimes used
to refer to base- O O
+
catalysed hydrolysis H
RCOH + R'OH RCOR ' + H2O
of any acid derivative.
acid alcohol ester
Base catalysed
hydrolysis of esters is In esterification, either excess of the starting alcohol is used or water produced
faster than acid- is removed from the reaction mixture to shift the equilibrium in the forward
catalysed hydrolysis. direction. But when ester hydrolysis is the objective, the reaction is carried out
using excess of water in the presence of a mineral acid. Remember that acid-
catalysed hydrolysis is an equilibrium process.
In contrast to acid catalysed hydrolysis, base catalysed hydrolysis of esters is

not an equilibrium process but is irreversible because the carboxylic acid
produced on hydrolysis is converted to its anion under the basic conditions.
O O
 
RCOR ' + HO RCO + R'OH
ester hydroxide carboxylate alcohol

ion ion
CH3 O CH3 O
1. KOH, H2O, CH3OH, 
CH 3CHCH 2COCH 3 CH 3CHCH 2COH + CH 3OH
+
2. H , H2O
methyl 3-methyl- 3-methylbutanoic methanol
butanoate acid
O OCH 3 O OH
C C
 1. 20% NaOH, 5-10 min.

+ HO + CH3OH
2. HCl
NO 2 NO 2
As shown in the above examples, a separate acidification step is required to

get the free acid from the carboxylate ion.
2. Reaction with ammonia and amines: Conversion to amides
Esters react with ammonia and amines to give an amide and an alcohol.
O O
RCOR ' + NH3 RCNH 2 + R'OH
46 ester ammonia amide alcohol
O O
heat + CH3CH 2OH
FCH 2COCH 2CH 3 + NH2 FCH 2CNH
ethyl fluoroethanoate cyclohexylamine N-cyclohexyl- fluoroethanamide ethanol

(61%)
The reaction of esters with azanol (hydroxylamine, :NH2OH) gives

N-hydroxyamides. These compounds are known as hydroxyamic acids.
O O
R C OCH 2CH 3 + :NH2OH R C NHOH + C 2H5OH
ester azanol a hydroxamic ethanol
(hydroxylamine) acid
The hydroxamic acids form highly coloured complexes with ferric ion. This
chemistry forms the basis of hydroxamic test used for the identification of
esters.
3. Reaction with alcohols: Transeterification
It was pointed out in the last sub-section that a new ester can be syhthesised
by the reaction of an ester with an alcohol by a process called
transesterification.
Transeterification is an equilibrium reaction and requires a large excess of the
alcohol which is usually used in the form of solvent.
O O
+
H
C17H35COCH2CH3 + CH3OH C17H35COCH3 + CH3CH2OH
or
_
ethyl octadecanoate solvent OCH3 methyl octadecanoate ethanol
4. Reaction with Grignard Reagents

Esters react with two equivalents of Grignard reagent to produce tertiary
alcohols.
O OH
1. ether
RCOR ' + 2 R"MgX + RCR " + R'OH
ester 2. H3O
Grignard reagent alcohol
R"
a tertiary alcohol
A ketone is an intermediate in the reaction but as soon as it is formed, it reacts

with the second equivalent of the Grignard reagent.
O O
ether
RCOR ' + R"MgX RCR " + ROMgX
ester ketone
1. R"MgX, ether
+
2. H3O
OH
R C R"
R"
a tertiary alcohol
47
Obviously, methanoic esters on reaction with Grignard reagents yield a

secondary alcohol. For example,
O OH
1. ether CH2CH2CH2CH3 + C2H5OH
HCOC 2H5 + 2 CH 3CH 2CH 2CH 2MgBr +
HC
2. H , H2O ethanol
ethyl n-butyl CH 2CH 2CH 2CH 3
methanoate magnesium
bromide 5-nonanol
(85%)
This reaction is a very important method for the synthesis of alcohols having
two identical groups attached to carbon atom carrying the hydroxyl group.
5. Reduction
The hydrogenation of esters is accompanied by cleavage to yield two alcohols

and is therefore, referred to as hydrogenolysis.
O
hydrogenolysis
RCOR' RCH2OH + R'OH
ester primary alcohol
alcohol
Hydrogenolysis is normally carried over a combination of copper-chromium

oxides known as copper chromite at high temperature and pressure.
O
H2 (200 atm)
COCH 2CH 3 CH 2OH + CH3CH 2OH
copper chromite
523 K ethanol
cyclohexylmethanol
ethyl cyclohexanecarboxylate
(97%)
The reduction proceeds in two stages. The first stage involves the formation of
on aldehydes which rapidly undergoes reduction to the primary alcohol.
O O
H2
RC OR' RCH + R'OH
catalyst aldehyde alcohol
(slow)
H2,
catalyst
(fast)
cleavage of this
bond on first
RCH 2OH
hydrogenation (a primary
alcohol)
Esters are also reduced by sodium in alcohol. This is a method of long

standing and is known as Bouveault-Blanc reduction. It was the common
laboratory method before the discovery of lithium aluminium hydride.
O
Na
CH 3(CH 2)10COCH 2CH 3 CH 3(CH 2)10CH 2OH + CH3CH 2OH
ethanol
dodecanol ethanol
ethyl dodecanoate
48 (65-75%)
Reduction of esters using lithium aluminium hydride requires only 0.5

equivalent of LiAIH4 because only two of the hydrogens are used per ester
function.
O
1. LiAlH4, ether
2 CH3CH2COCH3 +
CH3CH2CH2OH + CH3OH
2. H2O, H
1-propanol methanol
methyl propanoate
(92%)
This reduction proceeds via the formation of an aldehyde which reacts rapidly
with LiAlH4 and yields an alcohol after acidification.
6. Formation of Enolates You will study about

the Claisen
When esters are treated with strong bases at low temperature, ester enolates
condensation
are formed. This involves the abstraction of the acidic hydrogen from the involving ester
carbon atom next to the ester function. enolates to yield 3-
ketoesters such as

O O ethyl 3-oxobutanoate

RCH C + H B Unit 8 of BCHET-147
RCHCOR ' + :B
OR' Course.
H
ester ester enolate
Having studied the reactions of esters, answer the following SAQ.
SAQ 4
Write the expected product(s) of the reaction between ethyl benzoate and the
following reagents:
a) H+, H2O, heat
b) NaOH, H2O
c) Aqueous NH3, heat
d) i) LiAlH4
ii) H3O+
e) i) excess CH3CH2CH2MgBr
ii) H2O, H+
10.7 AMIDES
The amides can be named by replacing the -ic or -oic acid suffix of the
carboxylic acid with the suffix amide.
O O
CH 3C-OH CH 3C-NH 2
acetic acid acetamide
49
Thus, acetamide has the IUPAC name ethanamide. Having done this, can you
give common and IUPAC names for the following amide?
O
HC NH2
These are formamide and methanamide, respectively. The IUPAC name for
an amide is derived by appending the suffix amide to the parent hydrocarbon
with the final e dropped. Thus, amides can be named as alkanamides.
Amides are also named as substituted carboxamides. According to this

system, in
O
R C NH2
the name of the group R followed by the suffix carboamide gives the name of
the amide; examples being benzenecarboxamide and
cylcopentanecarboxamide.
O
O C NH2
C NH2
benzenecarboxamide cyclopentanecarboxamide
Amides can be classified as primary, secondary or tertiary according to the

degree of substitution on the amide nitrogen.
RCONH 2 RCONHR ' RCONR 'R"

a primary amide a seconday amide a tertiary amide
In the case of secondary and tertiary amides, the symbol N- must precede the
name of each different group attached to the nitrogen.
O
O
CH 3 C H C
N CH 2CH 3
NH
CH 3
N-phenylethanamide N-ethyl-N-methyl-methanamide
Cyclic amides are called lactams. The systematic names of some lactams are
given below:
O
 1
  NH
2
 2
1 O  
N 
H
2-azacyclopentanone 2-azacyclohexanone
50 (-butyrolactam) (-valerolactam)
10.7.1 Preparation of Amides

The formation of amides from carboxylic acid halides, anhydrides and esters
was discussed in Secs. 10.4.2, 10.5.2 and 10.6.2, respectively. General
reactions of the above carboxylic acid derivatives with amines (or ammonia)
can be represented as shown below:
O O H O
RCL + R'2NH R C L RCNR '2 + HL
carboxylic acid amine amide conjugate
NR'2 acid of the
derivative
tetrahedral leaving
intermediate group
You will recall that two molar equivalents of amine are required in case of
carboxylic acid halide and anhydride.
O O
+ 
2 R 2NH + R'CCl R'CNR 2 + R2NHCl
amine carboxylic amide hydrochloride
acid halide salt of amine
O O O O
+ 
2 R 2NH + R'COCR ' R'CNR 2 + R2NH OCR '
amine carboxylic acid amide carboxylate
anhydride salt of amine
But in the case of esters, no acid is formed. Therefore, the reaction is carried
out using the ester and the amine in 1:1 molar ratio to yield the amide.
O O
R2NH + R'COCH3 R'CNR 2 + CH3OH
amine methyl ester amide methanol
In addition to the above methods, amides can also be prepared from

ammonium carboxylates. Ammonium carboxylates are prepared by the
reaction of ammonia with carboxylic acids.
O O

:
R C OH + NH 3 R C ONH 4
an ammonium
carboxylate
When dry ammonium carboxylates are heated, dehydration takes place to

yield an amide.
O O
 heat
R C O NH 4 R C NH 2 + H2O
(solid)
A similar sequence of reactions can be carried out using amines instead of

ammonia. 51
This is a poor method of preparing amides. A much better method is to convert

the acid into the acid halide which can yield the amide as discussed above in
sub-Sec. 10.4.2.
You may recall from sub-Sec. 18.4.1, Unit 18, Block 4 of BCHCT-135 Course
that ketones react with RNH2 compounds to yield condensation products.
When azanol (hydroxylamine, HO–NH2) reacts with ketones, an oxime is
obtained as shown below.
R R OH
+
H
C O + H2N OH C N
H2O
R' R'
oxime
Oximes on heating with a strong acid rearrange to give amides.
R OH O
H2SO4
C N heat
R C NHR '
R'
oxime amide
This reaction is known as Beckmann rearrangement.
10.7.2 Reactions of Amides

The reactions of amides are listed in Table 10.8.
Table 10.8: Reactions of Amides
1. Hydrolysis
O O
+ H2O +
R C NR' + H3O R C OH + R' NH 2
R" R"
O O
 H2O 
R C NR' + OH R C O + R' NH
R" R"
R, R, and/or R may be H
2. Reduction
O
LiAlH4
R C NR'2 RCH 2NR'2
or B2H6
or
3. Dehydration
O
P2O5
R CNH 2 R C N
heat
(H2O)
4. Hofmann rearrangement
O
Br2, NaOH, H2O
R C NH2 RNH 2 + O C O
52
Amides are the least reactive amongst the carboxylic acid derivatives
discussed so far. Therefore, their nucleophilic addition-elimination requires
relatively vigorous reaction conditions. Let us understand this by taking the
example of hydrolysis.
1. Hydrolysis of Amides
Hydrolysis of amides occurs only on prolonged heating in strongly acidic or

basic aqueous conditions to yield an amine and a carboxylic acid.
O R' O R'
hydrolysis
RC N + H2O RCOH + N H
R" R"
amide water acid amine
When the hydrolysis is carried out in acidic medium, the amine obtained is
protonated to yield ammonium ion, i.e.,
O O H
+ +
R CNR' 2 + H3O RCOH + R ' N R'
H
an ammonium
ion
But when the hydrolysis is done using a base, the carboxylic acid obtained is
deprotonated to give a carboxylate ion, as shown below:
O O R'
 H2O 
RCNR' 2 + OH RCO + R' N
amide hydroxide carboxylate H
ion ion amine
The following examples illustrate hydrolysis of amides.
CH 3CH 2CHCNH 2 CH 3CH 2CHCOOH
H2O, H2SO4 +
+ NH4HSO4
heat
2-phenylbutanamide 2-phenylbutannoic amonium

acid (88-90%) hydrogen sulphate
O O

OH, H2O,  
CH 3CH 2CH 2CNHCH 3 CH 3CH 2CH 2CO + CH3NH 2
+
H , H2O
O

CH 3CH 2CH 2COH + CH 3NH 3
butanoic acid (87%) 53
2. Reduction of Amides
Amides can be converted to the corresponding amines on reduction with

lithium aluminum hydride.
O
1. LiAlH4
R C NR' 2 + RCH 2NR' 2
2. H2O, H amine
amide
O
1. LiAlH4, ether
(CH 3)2CHCH 2CH 2CN(CH 2CH 3)2 +
(CH 3)2CHCH 2CH 2CH 2N(CH 2CH 3)2
2. H2O, H
N, N-diethyl-4-methylpentanamide N, N-diethyl-4-methylpentanamine
(85%)
Diborane, B2H6, may also be used for the reduction of amides.

O
B2H6
(CH 3)3CCN(CH 3)2 (CH 3) 3CCH 2N(CH 3)2
THF
N, N, 2,2-tetramethylpropanamide N, N, 2,2-tetramethyl propanamine
(79%)
3. Dehydration of Amides
Amides can be dehydrated, using a number of dehydrating agents like P2O5 or

ethanoic anhydride, to the corresponding nitriles. For example,
O
P2O5
CH 3CH 2 C CH 3CH 2C N

H2O
NH2 propanenitrile
propanamide (55-70%)
4. Hofmann Rearrangement
O
Primary amides RCNH 2 , on treatment with bromine in basic solution undergo

an interesting reaction to yield amines.
O
Br 2,NaOH, H 2O
RCNH 2 RNH 2 + O C O
The overall reaction appears as if the carbonyl group is expelled from the
amide to give an amine with one carbon atom less than the amide.
O
Br2, NaOH, H2O
(CH 3) 3CCH 2CNH 2 (CH 3) 3CCH 2NH 2
3,3-dimethylbutanamide 2,2-dimethylpropanamine
(94%)
The reaction proceeds via the following steps.
Step 1: Amidate formation
: O: : O:
 
:
: :
: :
54 RCNH 2 + : OH RCNH + HOH

:
Step 2: Halogenation
: O: : O:
:  
: :
:
:
RCNH + :X X: RCNH + : X:
:
:
: X:
:
Step 3: N-Halo amidate formation
: O: O


:
: :
:
RCNH + : OH RCN X: + HOH
:
:
N-haloamidate
: X:
:
Step 4: Halide elimination
: O: : O:
 
:
:
:
:
RCN X: RCN + : X:
:
:
:
:
Step 5: Rearrangement
:O :
:
C O C N
:
R N: R
an isocyanate
Step 6: Hydrolysis to carbamic acid and decomposition
:O :
H
H2O
:
:
:
N C O N C OH RNH 2 + CO2
:
:
R R amine
After studying the chemistry of amides, answer the following SAQ.
SAQ 5
Outline the synthesis of propanamine, CH3CH2CH2NH2 from butanoic acid.
10.8 SUMMARY
In this Unit, you have studied that
 the functional derivatives of carboxylic acids are those derivatives which

are formed by substitution of -OH of the carboxy group and can be
hydrolysed to yield carboxy acids.
 various carboxylic acid derivatives can be arranged according to their

reactivity in the following order:
carboxylic acid > carboxylic acid > esters > amides

halides anhydrides 55
 the electrophilic reactivity of the carbonyl carbon in carboxylic acid

derivatives is weakened by good electron-donating substituents. This
also explains the increasing basicity in the series: carboxylic acid halides
< anhydrides < esters < amides.
 carboxylic acid derivatives undergo nucleophilic substitution reactions by

addition-elimination mechanism.
 one carboxylic acid derivative can be converted into another by

nucleophilic addition-elimination and the more reactive derivative can be
converted to the less reactive derivative easily but the reverse requires
special conditions and suitable catalysts.
 carboxylic acid halides undergo nucleophilic substitution reactions with

water, carboxylic acids, alcohols, amines and organometallic reagents.
 reactions of carboxylic acid anhydrides with water, alcohol and amines

are similar to carboxylic acid halides.
 esters can be obtained from carboxylic acids, carboxylic acid halides and
carboxylic acids anhydrides by reaction with alcohols.
 esters can be hydrolysed both in acidic and basic conditions and they
react with amines to yield amides and alcohols. Their catalytic
hydrogenation, reaction with Grignard reagents and LiAlH4, yield
alcohols.
 Amides can be prepared by the reaction of ammonia or amines with

carboxylic acid halides, anhydrides and esters. Their important reactions
include hydrolysis, reduction, dehydration and Hofmann rearrangement.

1. Benzenecarboxylic anhydride can be prepared by adding one molar
equivalent of water to two molar equivalents of benzenecarbonyl
chloride, i.e.,
O O O
C Cl C O C
2 + H2O
benzenecarbonyl chloride benzenecarboxylic anhydride
Explain how this reaction takes place.
2. Write products of the following reactions
CH3OH
a) O
373 K
O
butanedioic
anhydride
56
O
H3C
2 NH3
b) O
H3C
O
3,3-dimethylpentanedioic
anhydride
3. The compound
O O
CH3COCH2CHCH2CH2CH2OCCH3
OCCH3
O
on hydrolysis in acidic medium gave a compound of molecular formula

C5H12O3. Write the structure of this compound. What other compound is
formed in this reaction?
4. Suggest suitable starting materials for the following reactions.

O
? + ? (CH 3)2CHCNH 2
a)
an acid
halide
? + ? CH 3CNHCH 3
b)
an acid
anhydride
? + ? HCN(CH 3)2
c)
a methyl
ester
5. Write the products of hydrolysis of the following compounds.

O CH 2CH 3
C N
a) CH 2CH 3
CH 2
O
CH2 C
b)
CH2 N H
CH 2
O
HOOCCH2 NHC CHNH 2
c)
CH2
CH3
57
10.10 ANSWERS
Self-Assessment Questions
1. a) Amide
b) Alkanoyl halides
2. a) H2O
O
 +
b) CH 3CO Na
OH
c)
d) (CH3)2NH
e) (CH3CH2)2Cd or LiCu(CH3CH2)2
f) LiAl[OC(CH3)3]3H or H2, Pd–BaSO4, Quinoline
3. a) O
2 CH3COH
ethanoic acid
O O
b) CH 3CH 2COCH 3 + HOCCH2CH 3
methyl propanoic
propanoate acid
O O
CNHCH(CH3)2 HOC
c) +
N-(1-methylethyl)- cyclohexanecarboxylic
cyclohexanecarboxamide acid
4. O
C O CH 2CH 3
ethyl benzoate
COOH
H+, H2O, heat
a) + CH3CH 2OH
58
O
 +
C O Na
NaOH, H2O
b) + C2H5OH
O
C NH2
aq. NH3, heat
c) + CH3CH 2OH
CH 2OH
1. LiAlH4
d) + CH3CH 2OH
2. H2O, H+
1. excess CH3CH2CH2MgBr
2. H2O, H+
e) OH
C CH 2CH 2CH 2CH 3
+ CH 3CH 2OH
CH 2CH 2CH 2CH 3
O
1. SOCl2 Br2, NaOH
5. CH 3CH 2CH 2COOH CH 3CH 2CH 2CNH 2 CH 3CH 2CH 2NH 2
2. NH3 H2O
butanoic acid butanamide propanamine
Terminal Questions
1. Benzenecarbonyl chloride on reaction with water yields
benzenecarboxylic acid which further reacts with second molar
equivalent of benzenecarbonyl chloride to yield benezenecarboxylic
anhydride.
O O
2. a) HOCCH 2CH 2COCH 3
O CH3 O
+ 
b) NH 4 OCCH 2CCH 2CNH 2
CH3
3. HOH 2CCHCH 2CH 2CH 2OH

OH
(molecular formula C5H12O3)
The other product obtained is ethanoic acid.

O
4. a) (CH3)2CHCCl and 2 NH3
O O
b) CH3COCCH3 and 2 CH3NH 2
59
O
c) HCOCH3 and HN(CH 3)2
O
5. a) COH
+ NH(CH 2CH 3)2
b) H2NCH2CH2CH2CH2COOH
c) HOOCCH 2 NH 2 + HOOCCH NH2
CH 2
CH 3
60
Unit 11 Amines
UNIT 11
AMINES
Structure
11.1 Introduction 11.5 Reactions of Amines
Expected Learning Outcomes As Bases
11.2 Structure and Reactivity of As Nucleophiles
Amines
Hofmann Elimination
Structure of Amines
Schotten-Baumann Reaction
Reactivity of Amines
Reaction with Nitrous Acid
11.3 Physical Properties of Amines Oxidation of Amines
11.4 Preparation of Amines 11.6 Electrophilic Substitution of
Direct Alkylation of Ammonia and Aniline:
other Amines by Alkyl Halides
Bromination
Indirect alkylation: The Gabriel
Nitration
Synthesis
Sulphonation
From Amides
Reduction of Nitriles 11.7 Laboratory Detection of
Amines
Reduction of Imines
11.8 Uses of Amines
Reduction of Oximes
11.9 Summary
Reduction of Nitro
Compounds 11.10 Terminal Questions
11.11 Answers
11.1 INTRODUCTION
Amines represent one of the largest classes of nitrogen containing organic
compounds. You are aware that amines are compounds in which one or more
alkyl or aryl groups are attached to nitrogen. In this unit, you will first study
about the importance and structure of amines. Then, a brief account of the
physical properties of amines such as molecular weight, melting point and
boiling point, will be presented.
You may have studied earlier that nitro compounds can be reduced to amines.
Here, we will discuss various methods of preparation of amines. After this, the
important reactions of amines will be explained.
61
Because of the pair of non-bonding elections on the nitrogen atom, amines are
important organic bases. They behave as nucleophiles as you have studied in
their reactions with carboxylic acid derivatives in Unit 10. They react with
nitrous acid which is electrophilic in nature. The reaction of primary aromatic
amines and nitrous acid gives diazonium salts about which you will study in
Unit 12. The diazonium salts are important because they can lead to a large
variety of organic compounds. Finally, you will study about the uses of amines
and methods employed for the detection of amines in the laboratory.

 explain the importance of amines;
 classify amines as primary, secondary or tertiary;
 give systematic (IUPAC) names of amines;
 correlate the physical properties of amines with their structures;
 outline the syntheses of amines using various methods;
 describe the reactions of amines;
 list some important amines and their uses; and
 give methods of detection of amines in the laboratory.

The term alkaloid
was coined by F.W.A.
Serturner who in 11.2 STRUCTURE AND REACTIVITY OF AMINES
1816, described
morphine as basic Amines are widely distributed in nature. A large class of amines of plant origin
and alkali like.
is called alkaloids. Strychnine and brucine, which you studied in Unit 11,
Sec.11.4 of BCHCT-131 course for the resolution of enantiomers, are
alkaloids. Some of the alkaloids have medicinal while others have poisonous
properties. Examples of such alkaloids include quinine, which is antimalarial
and antimicrobial, caffeine and atropine which are used as stimulants.
The alkaloids occurring in mammals include many essential vitamins and

hormones. Some examples are shown below.
CH 3
F.W.A. Serturner NH2 
H OH Cl CH 2CH 2OH CH 2NH 2
(19 June 1783 to C CH 2 N
+
HO HO CH 2OH
20 Februrary 1841) CH 2 N S
NHCH 3
HO CH 3 N CH 3 N
adrenaline vitamin B1 pyridoxamine
(a hormone secreted (thiamine chloride) (one of the complex
by adrenal glands) B6 vitamins)
Amines can be classified as primary, secondary or tertiary depending on the

number of alkyl or aryl groups attached to the nitrogen atom. When the
substituents attached to the nitrogen are alkyl groups, the amine is called an
alkyl amine. But the amines in which at least one of the substituents attached
62 to the nitrogen atom is an aryl group, are called aryl amines or anilines.
Unit 11 Amines
Some examples of primary, secondary and tertiary, alkyl as well as aryl

amines along with their names are given below:
CH3 CH3
CH 3 NH2 CH 3 CH NH2 CH 3 C NH2

methylamine or 2-propanamine CH3
methanamine
1,1-dimethylethanamine
a primary alkyl amine a secondary alkyl amine a tertiary alkyl amine
NH2 NHCH 3 CH 3NCH 3
benzenamine N-methylbenzenamine N,N-dimethylbenzenamine

(aniline) (N-methylaniline) (N,N-dimethylaniline)
There are two systems of naming amines. One method names them as
alkylamines and the other calls them as alkanamines as shown above. The
alkanamines naming system was introduced by Chemical Abstract Services
and is easier to use as compared to the earlier IUPAC system of alkylamine
names.
The latest revision of IUPAC rules accepts both systems and examples below
are named in both the ways.
4 3 2 1
CH3NH 2 CH3CH2CH2CH NH2
methylamine or
methanamine
CH3
1-methylbutylamine
or 2-pentanamine
Note that the numbering starts at the carbon atom and not at the nitrogen of
the amine part in the chain.
Primary diamines are named by using the suffix diamine after the name of the
hydrocarbon.
NH2
1 2 3 4
H2N CH2 CH2 CH2 CH2 NH2 H3C CH2 CH2 CH CH2NH 2
5 4 3 2 1
1,4-butanediamine 1,2-pentanediamine
For the secondary and the tertiary amines, the longest alkyl group present is
considered as the parent chain. The remaining alkyl groups are named as
substituents attached to the nitrogen and a prefix N- is used with the name of
the alkyl group.
1 2
H3C NH CH3 CH3NH CH2CH3
N-methylmethanamine N-methylethanamine
(common name: dimethylamine) (common name: ethylmethylamine)
63
CH3 CH3
2 1 1 2 3
CH3CH2 N CH3 CH3CH2CH2 N CH2CH2CH3
N,N-dimethylethanamine N-methyl-N-propylproanamine
(common name: ethyldimethylamine) (common name: methyldipropylamine)
1 2 3
CH3CH2CH2 N CH3
CH2CH3
N-ethyl-N-methylpropanamine
(common name: ethylmethylpropylamine)
When used as a substituent, the –NH2 group is named as amino and is

prefixed with a number indicating the carbon atom to which it is attached.
CH3
2 1 2 1
H2N CH2 CH2OH CH3 NCH2COOH
2-aminoethanol N,N-dimethylaminoethanoic acid
You check now your understanding about the nomenclature of amines by

answering the following SAQ.
SAQ 1
Write IUPAC names of the following amines:
CH3
i) CH3CHCH2NH 2 ii) (CH3CH2)3N
iii) NH2 iv) H2NCH 2CHCH 3
NH2
v) NH2
NO 2
Let us now study about the structure and reactivity of amines.
11.2.1 Structure of Amines

You may recall from your earlier studies that ammonia has a pyramidal shape.
The HNH angle in ammonia, 107.3, is very close to the angle of a
tetrahedron. Hybridisation in ammonia can thus be described as nearly sp3.
The structure of amines is similar to the structure of ammonia. Aliphatic

amines have a pyramidal shape or if we regard the lone pair of electrons as a
group, an approximately tetrahedral shape. The three vertices of the
tetrahedron are occupied by three substituent groups and the fourth is
64 occupied by the lone pair.
Unit 11 Amines
If the three substituents are different, then the nitrogen is chiral. This leads to
the possibility of existence of enantiomers. The enantiomers of
N-methylethanamine are shown in Fig. 11.1.
The nearly tetrahedral

structure of
methanamine
(methylamine)
Fig. 11.1: Enantiomers of N-methylethanamine.
But, in the absence of steric factors, amines undergo a rapid inversion at

nitrogen via a planer transition state to yield their enantiomers, as is shown in
Fig. 11.2. So it is not possible to isolate the enantiomers.
The melting point

increases with the
increase in the
molecular weight. This
can be explained due to
increase in the London
forces between the
larger molecules of
Fig. 11.2: Inversion at nitrogen interconverts the enantiomers of higher molecular weight.
N-methylethanamine. Thus, each additional
methylene (-CH2) unit
Since such an inversion is not possible in quaternary ammonium compounds, contributes to the
they can be separated into enantiomers. The enantiomers of such a increase in melting
point.
quaternary ammonium ion are shown below:
154 pm 147 pm
H
CH3 CH2
CH3 CH3 N
110o
+ + ethylamine
H
N N
C 2H 5 C6 H5 C 6H 5 C2 H5
CH 2CH=CH 2 CH 2=CHCH 2 m
147 p N H
CH3
108o - 111o
CH3
(S) (R)
dimethylamine
Aryl amines have larger HNH and HNC angles indicating that nitrogen in aryl
140 pm
amines is more nearly planer than in alkylamines. In aryl amines, the lone pair 119.5o N
100
pm H
of electrons is delocalised with the π electrons of the aromatic ring. The
o
HNH=130
resonance structures, thus, obtained are shown below for benzenamine. H
benzenamine
 (aniline)
:
 
:  
:
NH2 NH 2 NH 2 NH 2
:
You can see the double bond character of C-N bond in some of these
resonance structures. Thus, CN bond in benzenamine is shorter (140 pm) as
compared to that in aliphatic amines (147 pm). 65
The branched molecule

11.2.2 Reactivity of Amines
has a substantial
symmetry, therefore its Since amines contain a lone pair of electrons on the nitrogen atom, they can
melting point is relatively behave both as bases and nucleophiles. You will study about their behaviour
high. This can be
as bases and nucleophiles under their reactions in Sec 11.5.
explained by the fact
that the symmetrical
But before understanding these properties of amines, let us first study the
molecules fit together
more easily in the physical properties of amines and try to relate them to the structure of amines.
crystal lattice and
hence, have higher
melting points as
11.3 PHYSICAL PROPERTIES OF AMINES
compared to the less
symmetrical molecules. The physical constants of some amines are given in Table 11.1.
Table 11.1: Physical constants of amines

You can clearly
visualise certain trends Amine Molecular weight Melting point/K Boiling point/K
in the physical constants
Primary amines
of amines as listed in
Table 11.1. CH3NH2 31 179 277
CH3CH2NH2 45 192 290
CH3 CH2CH2NH2 59 190 321

In a homologous series,
the higher the molecular CH3 CH2CH2CH2NH2 73 224 351
weight, the larger will be
the molecules and the
(CH3)2CHCH2NH2 73 188 341
greater will be the area
(CH3)3CNH2 73 206 318
of contact between the
two molecules and aniline, C6H5NH2 93 267 467
hence, the greater will
be the London forces. o-nitroaniline 138 345 557
m-nitroaniline 138 387 579

In a homologous series, p-nitroaniline 138 421 605
the boiling points of the
compounds increase Secondary amines
with the increase in the
(CH3)2NH 45 181 280
number of carbon
atoms. In other words, (CH3CH2)2NH 73 223 329
we can say that the
boiling point increases 71 275 336
with increase in
molecular weight. N
Generally, this increase H
in boiling point amounts
0
to 20-30 for the N-methylaniline 107 216 469
addition of each carbon
N-ethylaniline 121 210 478
atom in the molecule.
The increase in boiling diphenylamine 169 327 575
point with molecular
weight can be again Tertiary amines
attributed to increased
trimethylamine, (CH3)3N 59 156 276
London forces of
attraction between triethylamine, (C2H5 )3N 101 159 363
larger molecules.
N,N-dimethylaniline 121 276 467
triphenylamine 245 400 638

66
Unit 11 Amines
The physical constants of the amines listed above in Table 11.1 show that
most amines are liquids. Amines generally have unpleasant fishlike odours.
Primary and secondary amines can participate in intermolecular hydrogen

bonding. The NH...H hydrogen bonds are weaker than OH...O hydrogen
bonds because nitrogen is less electronegative than oxygen. Thus, the boiling
points of primary amines are intermediate between those of alcohols and
alkanes of comparable molecular weight. The hydrogen bonding is also a
factor governing the water solubility of amines.
Among isomeric
SAQ 2 molecules, since the
unbranched isomer is
The melting point and boiling point of 2-nitrobenzenamine (o-nitroaniline) are linear and hence
extended in shape, it
lower than its 3-nitro (meta-) or 4-nitro (para-) isomer. Why?
has larger surface
area as compared to
Spectral Characteristics of Amines the branched isomer.
Therefore, London
UV spectra forces are stronger in
the unbranched
The absorptions due to n * transitions of saturated amines occur at short isomer leading to
higher boiling point
wavelengths (~ 220 nm) and, therefore, are not of much use for identification for this isomer.
purposes.
IR spectra
The infrared spectra of primary and secondary amines show a characteristic

broad bond due to NH stretching absorption in the region between 3300 and
3500 cm1, see Fig. 11.3. Primary amines show two bands in this region
whereas secondary amines show only one band. The NH bending absorption
of primary amines is observed near 1600 cm1.
Fig. 11.3: IR spectrum of butanamine.
NMR spectra
The HCN protons of alkylamines show absorption in the range  2.5-3.0.

The absorption occurs further downfield in aromatic amines, i.e., near  3. The
chemical shift of the N-H proton, like that of the O-H proton in alcohols,
depends on the concentration of the amine and on other factors such as
solvent and temperature. The NH proton also undergoes chemical exchange
as is observed in case of OH protons of alcohols. 67
The NMR spectrum of N-ethyl ethanamine is shown below in Fig. 11.4. You
can see the following peaks in the spectrum.
 3.0 (q)
0.9 (s) 1.0 (t)
NH CH2 CH3
 3.2 (s)  1.1 ( CH 3CH 2 NH CH 2 CH3

 7.87 H H  6.57
2.6 (q)
O 2N NH2
Fig. 11.4: The NMR spectrum of N-ethylethanamine.
The absorption of protons of aromatic ring ortho- and para- to the amino
meta-protons indicating the
nitrogen is shifted to higher field than that of the meta-
increased electron density at the ortho- and para-positions.
Mass spectra
The mass spectra of primary aliphatic amines show a peak atm/z = 30 due to
the following fragmentation from the M+ ion:
+. . +
RCH 2 CH2 NH2 RCH 2 + CH2 NH 2
m / z = 30
For example,
.. +. -cleavage
e
C2H5 CH2 CH2 NH2 C2H5 CH2 CH2 NH2
. +
C2H5 CH 2 + CH2 NH 2
m / z = 30
After understanding the physical and spectral properties of amines, you will
now study about different methods of preparation of amines.
11.4 PREPARATION OF AMINES

The various methods used for the preparation of amines are discussed below:
11.4.1 Direct Alkylation of Ammonia and Other

Amines by Alkyl Halides
Ammonia and amines react with alkyl halides to yield amines. Let us
understand this reaction with the example of ammonia and a primary alkyl
68 halide.
Unit 11 Amines
+ 
RX + NH 3 RNH 3X
alkyl ammonium halide
This reaction follows the SN2 path. If excess of ammonia is not used then the
reaction stops at the stage of alkyl ammonium halide. In the presence of
excess ammonia, another molecule of ammonia deprotonates the alkyl
ammonium ion thereby liberating the free amine.
+  + 
RNH 3X + NH3 RNH 2 + NH4X
alkyl ammonium ammonia amine ammonium
halide halide
The resulting amine being a nucleophile reacts further with alkyl halide to yield
dialkyl amine, trialkyl amine and quaternary ammonium salts as shown below. A secondary amine is
a stronger
+ 
RNH 2 + RX R2NH 2X nucleophile than a
dialkyl ammonium halide primary amine.
+  + 
R2NH 2X  + : NH3 R2NH  + NH4X
dialkyl amine
(a secondary amine)
+ 
R2NH + RX R3NHX
trialkyl ammonium halide
+  + 
R3NHX  + NH3 R3N: + NH4X
trialkyl amine
(a tertiary amine)
+ 
R3N: + RX R4NHX
tetraalkyl ammonium halide
(a quaternary ammonium salt)
Thus, a mixture of products is formed which limits the synthetic value of this
reaction for the synthesis of primary amines. The over alkylation may be
suppressed by using a large excess of ammonia or amine provided the amine
is inexpensive and the desired product can be easily separated from the
reaction mixture. Some examples follow:
O O
H2 O + - + -
CICH 2COH + 2 NH 3 H3NCH 2CO + NH4Cl
298 K
chloroethanoic acid ammonia aminoethanoic acid ammonium chloride
1 equivalent 60 equivalent (glycine)
(65%)
+ 
CH 2Cl + NH2 CH2 NH + NH 3Cl
benzyl chloride benzenamine N-phenylmethylbenzenamine benzenamine

1 equivalent 4 equivalents (N-benzylbenzenamine) hydrochloride
(aniline hydrochloride)
In many cases, even after using a large excess of the amine or ammonia, only
moderate yields of desired amine are available. In such cases, indirect
methods which give better yields are employed. One such method is the
Gabriel synthesis which you will now study. 69
11.4.2 Indirect alkylation: The Gabriel Synthesis

Pure primary amines can be prepared conveniently if the nitrogen atom is
protected so that alkylation can take place only once.
Such a protected nitrogen is present in 1,2-benzenedicarboxylic imide.

Because the nitrogen atom has two adjacent carbonyl groups, the NH group is
acidic enough (pKa = 8.3) to be deprotonated using a mild base to yield a
nitrogen anion in a salt.
O O
K2CO3, H2O  +
:NH :N: K
O O
1,2-benzendicarboxylic imide potassium salt
(phthalimide) with nitrogen anion
The nitrogen anion is a good nucleophile and can undergo a wide variety of
nucleophilic substitution reactions. It reacts with alkyl halides to yield N-alkyl
derivative in good yield. N-alkyl derivative on acidic hydrolysis yields the
ammonium salt from which the free amine can be liberated by treatment with a
base.
Such a sequence of reactions can be used to prepare amines which are

difficult to prepare by simple alkylation of ammonia and is known as Gabriel
synthesis.
O O
 +
:N: K + R X N R + KX
O O O
, HCl, H2O OH + NaOH


+ RNH3Cl RNH2
H2O
OH
The use of the Gabriel synthesis is limited to primary and unbranched

secondary alkyl halides. However, tertiary alkyl halides undergo eliminations
under these conditions.
11.4.3 From Amides

i) You are aware from Unit 10, Sec. 10, sub-Sec. 10.7.2 that amides can
be reduced to amines, i.e.
O
LiAlH4
RCNH 2 RCH 2NH 2
amide amine
Depending upon the structure of the starting amide, primary, secondary or

tertiary amines can be synthesised. Note that the number of carbon atoms
70 present in the amine is same as in the starting amide.
Unit 11 Amines
ii) From Hofmann Bromamide Degradation

You can refer to the
You have studied in Unit 10, sub-Sec. 10.7.2 in the reactions of amides that details of the
mechanism of this
amides on treatment of bromine under basic conditions in the presence of
reaction in Unit 10,
sodium hydroxide yield amines which have one carbon atom less than the sub-Sec. 10.7.2.
starting amide.
The reaction is referred to as Hofmann rearrangement.
The general reaction of Hofmann rearrangement or Hofmann bromamide

degradation is shown below:
O
Br2, NaOH
RCNH2 RNH 2 + O C O
H2O
Similar transformation involving the reaction of an alkanoyl halide with sodium

azide,NaN3, to yield amines is known as Curtius rearrangement. This
reaction proceeds via the following steps.
O O O
CHCl3  +  rearrangement
: :
+ 
RCCl + Na N3 RC N N N: RCN:
NaCl N2
alkanoyl alkanoyl
azide nitrene
H2O
RN C O RNH 2 + O C O
The same sequence of reactions is observed when the starting material is a

carboxylic acid. A carboxylic acid when treated with sodium azide in acid
catalyst yields an alkanoylazide which finally yields the amine. This reaction is
known as Schmidt rearrangement. An example of Schmidt rearrangement is
shown below:
HN3, H2SO4, C6H6

CH3(CH2)16COOH CH3(CH2) 15CH2NH 2
octadecanoic acid heptadecanamine

(96%)
11.4.4 Reduction of Nitriles

Nitriles can be reduced to primary amines by catalytic hydrogenation or by the
reaction with LiAlH4.
H2/PdC
R C N RCH2NH2
or LiAlH4
1.LiAlH4 2. H+, H2O

CH3CH2CH2CN CH3CH2CH2CH2NH2
ether
butanenitrile butanamine
(57%)
H2 / Ni
CH 3CH 2CH 2CH 2CN CH 3CH 2CH 2CH 2CH 2NH 2
pentanenitrile pentanamine
(90%)
71
11.4.5 Reduction of Imines

Ammonia and primary amines condense with aldehydes and ketones to yield
imines as shown below:
R' R'
H2O
C O + NH 3 C NH
R R
aldehyde or ketone imine
R' R'
H2O
C O + R"NH 2 C NR"
R R
imine
General Reductive The carbon nitrogen double bond of an imine can be reduced by catalytic
Amination of a Ketone
hydrogenation to yield a primary or secondary amine.
R
C O + H2NR" R' R'
H2/Pt
R' CH NH 2
C NH
condensation
R R
R R"
imine a primary amine
C N + H2O
R'
R' R'
reduction H2/Pt
C NR" CH NHR "
R R R
R' C NHR " imine a secondary amine
R'
Some examples are given below:

H H
H2O H2 / Ni
CHO + NH 3 CH NH CHNH
H2O CH3CH2OH, 343 K,
pressure
benzenecarboxaldehyde imine phenylmethanamine
(benzaldehyde) (not isolated) (benzylamine)
(89%)
O
H2, Pt
(CH 3)2CHCH + CH 3CH 2CH 2CH 2NH 2 (CH 3)2CHCH 2NHCH 2CH 2CH 2CH 3
ethanol
2-methylpropanal butanamine (N-2-methylpropyl) butanamine
You can see that the carbonyl group is reduced in the above reaction and the
amine is alkylated; hence, the reaction is also known as reductive alkylation
or reductive amination.
What makes the reductive amination a useful synthetic procedure is that it can
be carried out in a single operation involving the hydrogenation of a solution of
the carbonyl compound and ammonia (or amine) in the presence of a catalyst
without isolating the intermediate imine.
11.4.6 Reduction of Oximes

It was pointed out in Table 18.5, Sub.-Sec. 18.4.1, Unit 18, Block 4 of
72 BCHCT-133 Course that aldehydes and ketones react with azanol
Unit 11 Amines
(hydroxylamine) to yield oximes. Oximes so obtained can be reduced with

LiAlH4 or sodium in alcohol to yield primary amines.
NOH NH2
Na
CH 3(CH 2)5CCH 3 CH 3(CH 2)5CHCH 3
C2H5OH
2-octanone 2-octanamine
oxime (62-69%)
11.4.7 Reduction of Nitro Compounds

Nitro compounds can be reduced with a variety of reducing agents.
Nitroalkanes can be converted to alkanamines as shown below:
NO 2 NH2
Fe, FeSO4
CH 3(CH 2)5CHCH 3 CH 3(CH 2)5CHCH 3
H2SO4, H2O
2-nitrooctane 2-octanamine
(90%)
The product of reduction of aromatic nitro compounds depends on the reaction

conditions employed. Catalytic reduction and reduction in acidic media yields
aromatic amines.
Catalytic hydrogenation is carried out by using platinum, palladium or nickel

as the catalyst.
NO 2 NH2
H2, Ni
nitrobenzene benzenamine
For reduction in acidic medium a metal and an acid is used. Usually iron or
zinc and hydrochloric acid are taken.
Cl Cl
1. Fe, HCl
2. NaOH
NO 2 NH2
1-chloro-4-nitrobenzene 4-chlorobenzenamine
Reduction of a nitro compound to an amine requires six equivalents of the

reducing agent, i.e.,
+ 
R NO 2 + 6 H + 6 e RNH 2 + 2 H2O
The reduction actually proceeds in a series of two-electron steps via the

nitroso compounds (RN=O) and N-substituted azanol (RNHOH) as
successive intermediates.
2 [H] 2 [H] 2 [H]

RNO 2 RN O RNHOH RNH 2
H2O H2O
73
NO 2 NO NHOH NH2
- + - + - +
2 e +2H 2 e +2H 2 e +2H
H2O H2O H2O
nitrobenzene nitrosobenzene N-phenylazanol benzenenamine
Reduction can be stopped at the N-substituted azanol stage when reduction is

carried out in neutral conditions using zinc and ammonium chloride.
NO2 NHOH
Zn, aq. NH4Cl

338 K
nitrobenzene N-phenylazanol
(62-68%)
N-phenylazanol obtained above can be oxidised to nitrosobenzene.
H
Na2Cr2O7, H2SO4
N OH N O
268 K
N-phenylazanol nitrosobenzene
(65-70%)
Reduction of nitro compounds in basic medium gives binuclear compounds.

Given below are the products of reduction of nitrobenzene in basic media.

O
As2O3, NaOH 1,2-diphenyldiazene oxide
N N (azoxybenzene)
Zn, NaOH
Zn, NaOH diphenyldiazene

2 NO 2 N N (azobenzene)
(8 equiv)
Zn, NaOH
Zn, NaOH 1,2-diphenyldiazene

NH NH
(10 equiv) (hydroazobenzene)
Selective reduction of the nitro group is also possible as shown below:
NO 2 NH2
NaSH
CH3OH, 
NO 2 NO 2
1,3-nitrobenzene 3-nitrobenzenamine
(79-85%)
74 Using the knowledge gained so far, answer the following SAQ.

Unit 11 Amines
SAQ 3
Write the products of reduction of the following amides with LiAlH4.
CH 3 O
i) C6H5CHCH 2CNH 2
3-phenylbutanamide
O
ii) CH3CH2CH2CH2CNHCH 2CH2CH2CH3

N-butylpentanamide
O
iii) CN(CH 3)2
N,N-Dimethylcyclohexane carboxamide
11.5 REACTIONS OF AMINES

Let us now study the reactions exhibited by amines.
11.5.1 As Bases
Amines behave as Lewis bases because of the presence of a nonbonding
electron pair on nitrogen. The amines react with a variety of acids by accepting
a proton.
+ 
:
RNH 2 + HA RNH 3 + :A
The aqueous solutions of amines are basic in nature due to the following
equilibrium.
Keq + 
:
RNH 2 + H2O RNH 3 + OH
where Keq is the equilibrium constant.
Keq is related to the basicity constant, Kb, by the following expression.
+ 
[RNH 3] [OH ]
Kb = Keq [H2O] =
:
[RNH 2]
Also,
pKb = log Kb
It is convenient to refer to the base strength also in terms of the dissociation

constant, Ka, of the corresponding ammonium ion, i.e.,
+ Ka +
:
RNH 3 + H2O RNH 2 + H3O

where
+
:
[RNH2] [H3O ]
Ka =
+
[RNH3]
75
The pKa values of some typical ammonium ions are given in Table 11.2.
Table 11.2: Basicities of some ammonium ions in terms of pKa values
Ammonium ion pKa Ammonium ion pKa

+
CH 3NH 3 +
10.62 NH2 4.62
+
(CH 3)2NH 2 +
10.64 NH 2CH 3 4.85
+
(CH 3)3NH +
9.76 NH(CH 3)2 5.06
+
C2H5NH 3 +
10.63 CH 3 NH 3 5.07
+
(C 2H5)2NH 2 +
10.98 O2 N NH 3 1.11
+ 10.65
(C 2H5)3NH
Using your knowledge about various factors affecting the basicity, you can
observe the following trends in the pKa values given in Table 11.2.
Quaternary i) Increasing alkyl substitution at the nitrogen in the amine leads to an
ammonium salts are
useful in synthetic increase in the basicity.
organic chemistry as
phase transfer ii) Lower pKa values and higher basicity of tertiary amines in aqueous
catalysts. Quaternary solution as compared to primary and secondary amines were explained
ammonium as due to the effect of poor solvation of the resulting substituted
hydroxides are ammonium ion in Unit 13. Block 3 of BCHCT-131 course.
particularly used as
substrates in iii) The electron-donating substituents such as CH3, OCH3 etc. increase
elimination reactions
to yield alkenes. the basicity whereas electron-withdrawing substituents such as Cl,
CN, NO2 etc. decrease the basicity.
iv) Since the electron pair on nitrogen is delocalised into the aromatic ring,
benzenamine (aniline) is less basic than ammonia, (see sub-Sec. 11.2.1
for resonance structures of aniline).
11.5.2 As Nucleophiles
The amines act as nucleophiles in alkylation and alkanoylation reactions.
Alkylation Reactions
It was pointed out in sub-Sec. 11.4.1 that alkyl halides react with primary
amines to yield secondary amines, tertiary amines and quaternary ammonium
salts. The mixture of amines thus obtained is then separated into individual
76 amines. This reaction has practical value on an industrial scale.
Unit 11 Amines
Alkanoylation Reactions
The alkanoylation reactions of amines with carboxylic acid derivatives to yield

amides were discussed in Unit 10, sub-Secs. 10.4.2, 10.5.2, 10.6.2 and in Unit
17, sub-Sec. 17.7.1. The general reaction can be represented as given below:
 
O O O O
+
H 
:
R C L + R'NH 2 R C L R C L R C NHR' + L
amide
NH 2R' NHR'
+
O
where L = halogen, O C R or OR.
11.5.3 Hofmann Elimination
You have studied above that alkylation of amines yields ultimately quaternary
ammonium salts as the reaction continues by repeated alkylation steps.
These quaternary salts undergo bimolecular -elimination reaction in the

presence of a strong base to give an alkene as the trialkyamine leaves as a
neutral leaving group. This is shown below:
+ - Ag2O, H 2O August Wilhelm von
CH 3CH 2CH 2CH 2N (CH 3)3I CH 3CH 2CH = CH 2 + H2O + N(CH 3)3 Hofmann
 th
(8 April1818 –
1 - butyltrimethylammonium iodide trimethyl th
alkene 5 May1895)
amine
(a quaternary salt)
Wet silver oxide is a source of –OH ions. These –OH ions abstract the proton
from the carbon  to the nitrogen.
+
N (CH 3)3
H
 
CH3CH2 C C H CH 3CH 2CH = CH 2 + H2O + N(CH 3)3
H H
-
OH
This type of elimination reaction is called Hofmann elimination.
Note here that the less substituted alkene has formed. Therefore, this reaction
is regioselective .
You can understand this in the light of the Hofmann rule. Since the
(trialkylammonium) nitrogen carrying three alkyl groups is a bulky group, it
hinders the approach of the base (–OH ion) from this end. Hence, the less
hindered proton in the molecule from the other end of the other carbon
( carbon) is abstracted by the base.
The Hofmann elimination has been useful in the structure elucidation of many
natural products which contain amino nitrogen. The amine is first completely 77
methylated using excess of iodomethane. This step is called exhaustive

methylation and yields a quaternary ammonium salt. The Hofmann elimination
of the ammonium salt as explained above yields the alkene. From the
structure of the alkene obtained, the position of the amino group in the starting
compound can be determined.
SAQ 4
Predict the product of Hofmann elimination of
CH 3 CH 2CHCH 3
+ -
N(CH 3) 3 OH
11.5.4 Schotten–Baumann Reaction

This reaction is named after Carl Schotten and Eugen Baumann who were
German chemists. The reaction was reported in 1884 by Schotten and was
extended by Baumann in 1886.
The reaction involves the benzoylation of the amine (or a phenol) in the
Carl Schotten presence of aqueous sodium hydroxide. Thus, aniline on benzoylation using
(12th July 1853-9thJan. 1910)
benzoyl chloride yields the amide (anilide) as given below:
NH2 COCl NH CO
aq. NaOH
+
aniline benzoyl phenyl benzamide

chloride (benzanilide)
Eugen Baumann
(12thDec.1846-3rdNov. 1896) COCl
+ aq. NaOH CO N
N
H
piperdine
(azacyclohexane)
Tertiary amines clearly do not undergo this reaction.
Schotten- Baumann reaction in which benzene sulphonyl chloride has been

used for sulphonylation yields sulphonamides. The formation of such
sulphonamides and their solubility behavior in a base forms the basis of the
Hinsberg test about which you will study in Sec. 11.7.
SAQ 5
Having understood the Schotten- Baumann reaction, can you predict its
mechanism?
78
Unit 11 Amines
11.5.5 Reaction with Nitrous Acid

Nitrous acid, HNO2, is a weak unstable acid. It is usually prepared in situ by
treating sodium nitrite with a strong mineral acid, usually hydrochloric acid at
273-278 K.
+  H2O + 
NaNO 2 + HCl HO N O + Na + Cl
273 K
nitrous acid
In strongly acidic solutions, nitrous acid gets protonated and then loses water
to give the nitrosoniumion.
H
+ +
HO N O + H 3O HO N O H 2O + N O
+
nitrous conjugate acid nitrosonium
acid of nitrous acid ion
The nitrosonium ion is electrophilic in nature and undergoes interesting

reactions with amines, called nitrosation reactions. The products of
nitrosation depend upon whether the amine is primary, secondary or tertiary
and whether it is aliphatic or aromatic. Let us now study each of them in detail.
i) Nitrosation of primary amines
Primary amines react with nitrous acid to yield diazonium salts via a number
of intermediate species. This reaction is called diazotisation. The evolution of
nitrogen during
Diazotisation of primary aliphatic amines yields alkyl diazonium salts. Alkyl
diazotisation is a
diazonium salts are unstable and decompose even at low temperatures to give good qualitative test
nitrogen and various other products via the intermediate carbocations. This is for aliphatic primary
explained in the following example. amines.
H2O
CH3CH2CH2CH2NH2 + NaNO2 + HCl
+  N2 +
[CH3CH2CH2CH2 N N:Cl ] CH3CH2CH2C H2
1-butanediazonium (a carbocation)
chloride
(a diazonium salt)
(highly unstable)
This carbocation yields a complex mixture of products as shown below:

CH 3CH 2CH 2CH 2Cl
(5%)
CH 3CH 2CH 2CH 2OH Cl CH 3CH 2CH CH2

H2O H+
(25%) (26%)
+
CH 3CH 2CH 2CH 2
rearrangement
+
CH 3CH 2CHCH 3
OH H2O Cl Cl
+
H
CH 3CH 2CHCH 3 CH 3CH 2CHCH 3
(13%) (3%)
CH 3CH CHCH 3
(10%)
(3% cis-isomer and 7% trans-isomer)
79
Nitrosamines are very

Diazotisation of primary aromatic amines leads to arenediazonium salts.
powerful Arenediazonium salts are more stable than alkyldiazonium salts and can be
carcinogens. stored at temperatures between 273 K and 278 K. Arenediazonium ions
Sodium nitrite, used undergo a variety of reactions and are versatile intermediates in the synthesis
as a preservative in
meats, and also the
of a variety of aromatic compounds about which you will study in detail in Sec.
nitrites, produced by 12.3 of Unit 12. However, the formation of an arenediazonium salt can be
the reduction of represented as shown below:
nitrate fertilisers,
react with natural + 
Ar NH 2 + 2 NaNO2 + 2 HX Ar N N:X + NaX + 2 H2O
amines in the
presence of acid primary arenediazonium
aryl amine salt (stable
found in stomach to
below 278 K)
yield nitrosamines.
Diemthylamine and ii) Nitrosation of secondary amines
ethylmethylamine are
found in tobacco Aliphatic and aromatic secondary amines react with nitrous acid to yield
smoke also.
N-nitroso compounds, also known as nitrosamines. Nitrosamines usually
separate from the reaction mixture as yellow oily liquids. Some examples of
the formation of nitrosamines are given below:
H
NaNO2, HCl, H2O + - HCl CH 3
(CH 3)2NH (CH 3)2N N O Cl N N O
273 K
N-nitrosammonium
chloride CH 3
N-nitrosodimethylamine
(88-90%)
CH3 NO
NHCH 3 N
NaNO2, HCl,
H2O, 273 K
N-methylbenzenamine N-nitroso-N-methylbenzenamine
(87-93%)
iii) Nitrosation of tertiary amines
Tertiary aliphatic amines react with nitrous acid without the evolution of
nitrogen to yield complex mixtures.
Tertiary aromatic amines react with nitrous acid to give C-nitroso aromatic
compounds. Nitrosation takes place almost exclusively at the para position of
the aromatic ring.
N(CH 2CH 3)2 N(CH 2CH 3)2
NaNO2, HCl, H2O

281 K
N,N-diethylbenzenamine
N
O
N,N-diethyl-p-nitrosobenzenamine
80 (95%)
Unit 11 Amines
11.5.6 Oxidation of Amines

Amines are sensitive to oxidising agents such as hydrogen peroxide, (H2O2)
O
and peroxy acids (RCOOH)

Oxidation of primary and secondary aliphatic amines yields complex mixtures.
Tertiary aliphatic amines, however, are oxidised to the corresponding amine
oxides. Some examples are given below:
CH3OH/H2O + -
(CH 3)3N: + 30% H2O2 (CH 3)3N O
trimethylamine oxide
(95%)

O
35% H2O2 +
:
C6H5CHNH(CH 3)2 C6H5CHN(CH 3)2

H2O
CH3 CH3
(98%)
Amine oxides on heating above 373 K yield N,N-dialkylhydroxylamine and an

alkene. This process is known as Cope elimination and is represented below:

O
+
H N(CH 3)2
R R 2C CR 2 + (CH3)2NOH
R
R R
N,N-dimethylalkylamine N-oxide alkene N,N-dimethylazanol
(N,N-methylhydroxyl amine)
Aromatic amines are easily oxidised by a variety of reagents including oxygen

in the air. The product of oxidation depends upon the temperature, pH and
amount of oxidising agent. Oxidation with hydrogen peroxide or peroxyacids
yields various products as shown below:
:
:
[:O:] [:O:]
NH2 NHOH
H2O
azanol
O
:
[:O:] +
N O N

O
nitroso nitro compound
compound
Oxidation of benzenamine using sodium dichromate in aqueoussulphuric acid

yields 1, 4-cyclohexadienedione.
NH2 O
Na2Cr2O7
H2SO4, 283 K
O
1,4-cyclohexadienedione
(para-benzoquione,
1,4-benzenedione) 81
11.6 ELECTROPHILIC AROMATIC SUBSTITUTION

OF ANILINE
The amino group activates the aromatic ring towards substitution by
electrophilic reagents. Aromatic amines like aniline undergo electrophilic
substitution reactions. The amino group is an ortho-, para– directing group.
Here, we will discuss interesting electrophilic reactions of aniline.
11.6.1 Bromination
Since the aromatic amines are very reactive, the halogenation of aniline such
as bromination in mild conditions yields tribromoaniline as shown below:
NH2 NH2
Br Br
+ 3 Br2 + 3 HBr
H2O
Br
However, if only ortho-, para- substituted products are desired, then the
reactivity of the -NH2 group is reduced by converting it into an acetamido
group. After such a protection, the desired electrophilic substitution reaction is
carried out followed by the deprotection which gives us the desired
monosubstituted product. We will discuss this strategy with examples at the
end of this section.
SAQ 6
What products will be obtained by the bromination of p-toluidine in aqueous
conditions?
11.6.2 Nitration
The nitration of aniline using nitric acid and sulphuric acid converts the amino

group to NH3 group. This group being positively charged, directs the
Since amino group is

susceptible to attack electrophile NO2 to meta position and meta-substituted product is formed in
by a wide variety of quite good amount, in addition to the para substituted product as in shown
reagents such as below:
oxidising agents,
NH2 NH2 NH2 NH2
alkylating reagents
and carbonyl NO 2
HNO3
compounds, it must + +
H2SO4, 20oC
be suitably protected.
NO 2
NO 2 (47%) (2%)
(51%)
The use of nitric acid
may lead to oxidation The formation of para product in these conditions may arise from the nitration
of aniline also. of very small amount of aniline present in the reaction mixture. It is also
possible that the reaction may undergo by a mechanism which is different from
the general mechanism of electrophilic aromatic substitution.
To get either only ortho- substituted product or para –substituted product,
82 again the strategy of first protecting the – NH2 group as –NHCOCH3 group is
Unit 11 Amines
used. The deprotection of –NHCOCH3 group is carried out to get back the –
NH2 group after electrophilic substitution. This will be illustrated with examples
at the end of this section. Let us now study the sulphonation reaction of
aniline.
11.6.3 Sulphonation
You already know that sulphonation of benzene is a reversible reaction. The
sulphonation of aniline is carried out by heating the anilinium hydrogen
sulphate. This salt is obtained by the reaction of aniline with sulphuric acid.
The main product obtained is sulphanilic acid as shown below:
+  +
NH2 NH 3HSO 4 NH 3
H2SO4

(180-200oC
aniline anilinium hydrogen  sulphanilic acid

sulphate SO 3
The sulphanilic acid so obtained is a zwitter ion.

Let us now address our desire to get either ortho- or para- substituted
products. Suppose we want to get only the para product, then we can start
with aniline and protect the amino group to get an anilide (I) in the first step.
NH2 NHCOCH3
O The reactivity of the
amino group is
CH 3CCl
reduced when it is
pyridine
(protection converted into an
of N of NH2 amide.
N-phenylethanamide
group) (an anilide, acetanilde)
(I)
C
20 o
Br 2
4
2 SO
,
FeB
H
r3
3,
O
HN
NHCOCH3
NHCOCH3
Br
NO 2
4-nitro-N-phenylethanamide Deprotection
(p-nitroacetanilide) 
OH, H2O, 
Deprotection
NHCOCH3
H2O, OH, 
NH2
Br
4-bromobenzenamine
(p-bromoaniline)
NO 2
4-nitrobenzenamine
(p-nitroaniline) 83
We then carry out the nitration or the bromination of (I) to get the 4- substituted
product. Finally, we carry out the deprotection or removal of the protecting
group to get the 4- nitro- or 4- bromo- substituted aniline. How to get an ortho-
substituted product?
Let us see an interesting sequence of reaction given below.
Starting from the acetanilide (I), we can take advantage of the reversible
nature of sulphonation reaction and carry out its sulphonation to give (II).
NHCOCH3 NHCOCH3
SO3, conc. H2SO4
N-phenylethanamide SO3H
(acetanilide)
(I) (II)
Now para position is blocked in it. If we carry out its electrophilic substitution,
say nitration, using HNO3, we will get electrophilic substitution at ortho
position, as given below:
NHCOCH3 NHCOCH3
NO2
HNO3
conc. H2SO4
SO3H SO3H
(II) (III)
1. H+, H2O, 
2. OH, H2O
NH2
NO2
(IV)
2-nitrobenzenamine
(o-nitroaniline)
From (III), we can get (IV), i.e. the ortho- substituted aniline by deprotection
and desulphonation.
SAQ 7
Predict the product of bromination of 3-nitro-N,N-dimethylbenzenamine.
84 Let us now understand how amines are detected in the laboratory.

Unit 11 Amines
11.7 LABORATORY DETECTION OF AMINES

Amines are characterised by their basic nature. They dissolve in dilute
aqueous acids. The elemental analysis of amines shows the presence of
nitrogen. In the laboratory, amines can be detected by using the following
tests.
1. Isocyanide (Carbylamine) test
Both aliphatic and aromatic primary amines react with chloroform in the
presence of potassium hydroxide to produce an isocyanide that has a very
nauseating odour. This reaction is so sensitive that it can be used as a test to
detect the presence of very small amounts of primary amines as impurities in
secondary and tertiary amines.
NH 2 + CHCl 3 + 3 KOH N C + 3 KCl + 3 H2O
Caution: You should destroy the isocyanide by heating the reaction mixture
with an acid before throwing the products into the laboratory sink
2. Reaction with nitrous acid
Amines can be characterised by their reaction with nitrous acid. The amine is
dissolved in dilute HCl and an ice-cold solution of sodium nitrite is added to it.
If a clear solution is obtained with the evolution of nitrogen, the amine is a
primary aliphatic or primary alkyl aryl amine. If no nitrogen is evolved, then
a cold solution of 2-naphthol in sodium hydroxide solution is added to a portion
of the above reaction mixture. If a colouredazo dye is formed, then the amine
is a primary aromatic amine.
If a yellow oily substance separates out when cold sodium nitrite solution is
added to the acidic solution of the amine, then the amine is a secondary
amine. The formation of the oily nitrosamine is confirmed by the Liebermann
nitroso reaction. The yellow oily substance is warmed with phenol and
concentrated sulphuric acid. Sulphuric acid liberates nitrous acid from
nitrosamine which reacts with phenol to yield p-nitrosophenol. The
p-nitrosophenol reacts with another molecule of phenol to yield red coloured
indophenol. In alkaline solution indophenol yields its anion which is blue in
colour. The sequence of reactions which occur can be represented as shown
below:
R R
H2SO4 C6H5OH C6H5OH
NNO NH + HNO 2 HO NO
R' R'
4-nitrosobenzenol
(p-nitrosophenol)
NaOH 
HO N O O N O
anion of indophenol
indophenol (blue)
(red) 85
If a dark orange-red solution is obtained on treatment of the amine with nitrous

acid and the colour changes to green on adding the alkali, then the amine is a
tertiary aromatic amine.
3. Hinsberg test
An efficient method to distinguish whether an amine is primary, secondary or

tertiary is the Hinsberg test. This involves the reaction between an amine
and benzene sulphonyl chloride in the presence of aqueous potassium
hydroxide.
Primary and secondary amines form substituted sulphonamides but tertiary

amines do not. The sulphonamides from the primary amine may be further
distinguished by the fact that it is soluble in potassium hydroxide, whereas the
derivative from the secondary amine, having no acidic hydrogen, is insoluble
in potassium hydroxide and, therefore, precipitates out.
The reactions involved with each type of amine are shown below:
acidic
H O H O hydrogen
OH
R N H + Cl S R N S
(HCl)
primary amine O O
KOH
+
H O K O
HCl 
:
R N S R N S
:
O O
water insoluble water-soluble salt
(precipitate) (clear solution)
R O R O
OH
R N H + Cl S R N S
(HCl)
:
secondary amine O O
water insoluble
(precipitate)
KOH
No reaction
H+
No reaction
R O (precipitate remains)
+ OH
R N R Cl S No reaction
tertiary amine
O
But amine will dissolve on acidification.

R R
HCl + 
R N: R N H Cl
R R
(insoluble) (soluble)
tertiary amine
86
Unit 11 Amines
SAQ 8
When 4-aminobenzenol reacts with one molar equivalent of ethanoic
anhydride, a compound having molecular formula, C8H9NO2 is formed which is
soluble in alkali. Write its structure.
11.8 USES OF AMINES

Amines have diverse uses. You have already studied most of them in this unit.
Let us now restate them
1. Several amines are physiologically active and are used as drugs.
2. Some naturally occurring amines, particularly alkaloids are used as

resolving agents for optically active compounds.
3. It was also pointed out that quaternary ammonium salts also act as
phase transfer catalysts. Quaternary ammonium salts are soluble in
both water and organic solvents and thus act as mediators for
reactions between species dissolved in immiscible liquids.
Quaternary ammonium salts having long chain alkyl groups such as 

hexadecyltrimethylammonium chloride, [C16H33N(CH3)3]+ Cl , have Cl
+
detergent properties. They are known as cationic surfactants or invert N
soaps because the surface-activity is found in a positive ion rather than
C 12H25
in a negative ion as is the case with ordinary soaps. dodecyl pyridinium
chloride
Most surface-active quaternary ammonium salts, such as dodecyl
pyridinium chloride are potent germicides.
Let us now summarise what we have learnt in this unit.
11.9 SUMMARY
In this unit, you have studied that
 Amines are nitrogen-containing organic bases.
 Amines can be classified as primary, secondary and tertiary according to

the degree of the substitution at the nitrogen atom.
 Amines have tetrahedral structure in which the nitrogen is sp3 hybridised.

One of the sp3 hybrid orbital is occupied by the unshared pair of electrons.
 Trends in the physical properties of amines such as melting and boiling

point can be explained on the basis of their molecular structure.
 Primary and secondary amines can be differentiated with the help of the
infrared spectra.
 Amines can be prepared by the following methods:
i) By alkylation using alkyl halides 87

R' R'
 NH 3
:
RNH 2 + R'X RNH 2X RNH
Drawback: multiple alkylation.
R'
+ 
RNH + R' X RNR 3' X
ii) Gabriel synthesis of primary amines

O O
K2CO3, H2O 1. H2SO4, H2O
:
NH NR RNH 2
RX 393 K
2. NaOH
O O
iii) From amides
a) By reduction
O
R' R'
LiAlH4
RCN RCH 2N
R" R"
b) By Hofmann rearrangement
O
Br2, NaOH, H2O
RCNH 2 RNH 2 + CO 2
Similar transformations starting with alkanoyl halides (Curtius

rearrangement) and carboxylic acids (Schmidt rearrangement) using
sodium azide also yield amines.
iv) By reduction of nitriles
LiAlH4
RCN RNH 2
or H2, Catalyst
v) By reduction of imines
R' R'
R'
H2O [H]
C O + NH 3 C NH R CH NH2
R R
aldehyde or ketone imine a primary imine
R' R'
R' H2O [H]
C O + R"NH 2 C NR" R CH NHR"
R R
aldehyde or ketone imine a secondary imine
88
Unit 11 Amines
vi) From oximes
O N OH NH2
NH2OH LiAlH4
RCR ' RCR ' RCR '
oxime H
a primary amine
vii) Reduction of nitro compounds
SN2 Fe/FeSO4

RX + NO 2 RNO 2 RNH2
X
 H+
R R R
HNO3/H2SO4 H2 / Ni
H2O 
NO 2 NH2
 Amines undergo the following reactions:
i) They behave as bases in aqueous solutions and form salts with

acids.
ii) They undergo alkylation with alkyl halides and alkanoylation with
carboxylic acids and their derivatives.
iii) Amines undergo Hofmann elimination to yield an alkene.
iv) Amines exhibit Schotten-Baumann reaction to give benzoylated

amines.
v) Tertiary aliphatic amines can be oxidised to amine oxides which

undergo Cope elimination on heating to yield an alkene and
N,N-dialkylhyroxylamine.
vi) Oxidation of aromatic amines leads to a variety of oxidation products

depending upon the oxidising agent and reaction conditions.
vii) Amines undergo nitrosation reaction with nitrous acid which gives
various products depending upon whether the amine is primary,
secondary or tertiary and is aliphatic or aromatic.
viii) The amino group activates the aromatic ring towards electrophilic
substitution reactions. The amino group is an ortho, para– directing
group. The bromination, nitration and sulphonation reactions of
amines were explained.
 Amines have various uses.
 Amines can be characterised in the laboratory by their reaction with

nitrous acid and Hinsberg test. 89

1. Name the following amines:
NH2 N(CH3)2
CH3
i) CH 3CHCH 2CH 3 ii) iii) BrCH 2CH 2CH 2CH 2CHNH 2
2. How will you carry out the following transformations?
a) CH 3O CH 3O NH2
b) CH 3O CH3O CHCH 3
NH2
c)
NO 2 CH3 NO 2 NH2
3. The Hofmann elimination of an amine yielded ethene and propene.

What could be its possible structure?
4. Complete the following reactions:
NHCOCH3 CH3
HNO3 SnCl2/HCl
a) b)
CH3COOH 
CH3 NO 2
CH3 N OH
NO 2
NaSH 1. LiAlH4
c) d)
CH3OH 2. H+, H2O
CH3
NO 2
5. Write the products of nitrosation of the following compounds.
i) NH2 ii) N(CH 3)2 iii) CH 2NHCH 3
6. What will happen to its solubility when sulphanilic acid is treated with
90
sodium hydroxide solution?
Unit 11 Amines
11.11 ANSWERS
Self Assessment Questions
1. i) 2-methylpropanamine
ii) N,N-diethylethanamine or triethylamine
iii) Cyclonexylamine
iv) 1,2-propanediamine
v) 3-nitrobenzenamine or 3-nitroaniline
2. Ortho-nitroaniline can undergo intramolecular hydrogen bonding whereas

its meta- and para- isomers show intermolecular hydrogen bonding. This
leads to lower melting and boiling points for ortho-nitroaniline.
3. i) CH3
C6H5CHCH2CH2NH 2
3-phenyl-1-butanamine
ii) CH3CH2CH2CH2CH2NHCH 2CH2CH2CH3

N-butyl-1-pentanamine
CH 2N(CH 3)2
iii)
N,N-dimethyl(cyclohexylmethyl)amine
4. CH3CH2CH=CH2
5. The mechanism involves the nucleophilic attack of the electrons of

nitrogen of the amino group at the carbonyl carbon of the benzoyl
halide.
-
O O
.. +
NH2 + Cl C NH2 C
Cl
-
This is followed by the removal of Cl as the leaving group.
-
O H O
+ +
NH2 C NH C
Cl
The loss of proton then yields the amide.

H
O O
+
+ -H
NH C NH C
91
6. NH2 NH2
Br Br
Br2 (aq)
CH 3 CH3
p-toluidine 3,5-dibromo-4-aminotoluene
7. N(CH 3)2 N(CH 3)2
Br2, 298 K
CH3COOH/NaOOCCH3
NO 2 NO 2
Br
8. OH OH
(CH3CO)2O
+ CH3COOH
NH2 NHCCH 3
O
mol. formula - C8H9NO2
Terminal Questions
1. i) 2-butanamine
ii) N,N-dimethylbenzenamine
iii) 6-bromo-2-hexanamine
HNO3/H2SO4
CH 3O CH 3O NO 2
2. a)
Fe/HCl
CH 3O NH2
O
CH3COCl/AlCl3
CH 3O CH 3O CCH 3
b)
NH2
1. NH3
CH 3O CHCH 3
2. H2/Ni
92
Unit 11 Amines
1. KMnO4/OH
c) NO 2 CH3 NO 2 COOH
2. H
O
SOCl2
NO 2 CCl
NH3
O
NaOH, Br2
NO 2 NH2 NO 2 CNH 2
3. These alkenes, ethene and propene could be formed by elimination of a

-hydrogen from ethyl and propyl substituents, respectively present in the
amine. So the amine could be CH3CH2CH2NHCH2CH3 which is
N-ethylpropanamine.
4. a) NHCOCH 3 NHCOCH 3
NO 2
HNO3
CH3COOH
CH3 CH3
b) CH3 CH3
SnCl2, HCl
+ 
NO 2 NH 3 Cl
c) CH3 CH3
NO 2 NH2
NaSH
CH3OH
CH 3 CH 3
NO 2 NO 2
d) N OH NH2
1. LiAlH4
2. H+, H2O
+ -
5. i) N2 Cl
a diazonium salt
93
ii) N(CH 3)2
NO
p-nitroso compound
NO
iii)
CH2 N CH3
N-nitroso compound
6. The insoluble dipolar sulphanilic acid will dissolve because sodium salt
i.e. sodium p-aminobenzenesulphonate will form. The strongly basic –OH

ions will abstract a proton from NH 3 of sulphanilic acid.
+
NH2 NH2

OH
+
SO3 SO3Na
Insoluble in water Water soluble
94
Unit 12 Diazonium Salts
UNIT 12
DIAZONIUM SALTS
Structure
12.1 Introduction
Formation of Aryl Fluorides
With Potassium Iodide
12.2 Preparation from Aromatic
Arylation
Amines
Conversion to Azo Dyes:
12.3 Reactions of Diazonium Salts
Coupling Reactions
Conversion to Phenols
12.4 Summary
Conversion to Benzene
12.5 Terminal Questions
The Sandmeyer Reaction
12.6 Answers
12.1 INTRODUCTION
In Unit 11, you have studied about the chemistry of amines. The reaction of
primary amines and nitrous acid gives diazonium salts. The diazonium salts
obtained from primary aliphatic amines are unstable but those formed by the
primary aromatic amines are stable. The diazonium salts are important
category of compounds which can be used to synthesise a large variety of
organic compounds.
In this unit, we will first discuss the methods of preparation of diazonium salts.
Then, the reactions of diazonium salts will be explained. These reaction are
useful in the synthesis of a variety of organic compounds. These compounds
have a variety of uses and especially the azo dyes obtained by the coupling
reactions of diazonium salts. Here, you will study about interesting examples
of azo dyes with which some of you might be already familiar.

 discuss the methods of preparation of diazonium salts;
 describe various reactions exhibited by the diazonium salts;
 explain the synthetic uses of diazonium salts;
 give some examples of azo dyes; and
 outline the synthesis of some important azo dyes.
95
12.2 PREPARATION FROM AROMATIC AMINES

In Unit 11, you have already studied that the products of nitrosation of amines
depend on whether the amine is primary, secondary or tertiary and whether it
is aliphatic or aromatic.
The nitrosation reactions are interesting reactions of amines wherein the

nitrosonium ion acts as an electrophile. As you have studied earlier in
sub-Sec.11.5.5 of Unit 11, the nitrosonium ion is obtained from the nitrous acid
as given below:
H2O
NaNO 2 + aq.HCl HO N O + NaCl
273 K
nitrous acid
H
+ +
HO N O + H3O HO N O H2O + N O
+
nitrous conjugate acid nitrosonium
acid of nitrous acid ion
In strongly acidic solutions, nitrous acid gets protonated and then loses water
to give the nitrosonium ion.
Nitrous acid, HNO2, is a weak unstable acid. It is usually prepared in situ by

treating sodium nitrite with a strong mineral acid, usually hydrochloric acid at
273-278 K.
The diazonium salts can be prepared by the nitrosation reaction of amines

with nitrous acid.
Nitrosation of Primary Amines
Primary amines react with nitrous acid to yield diazonium salts via a number
of intermediate species. This reaction is called diazotisation.
Diazotisation of primary aliphatic amines yields alkyl diazonium salts. Alkyl

diazonium salts are unstable and decompose even at low temperatures to give
nitrogen and various other products via the intermediate carbocation. This was
explained in Unit 11, sub-Sec.11.5.5.
H2O
CH 3CH 2CH 2CH 2NH 2 + NaNO 2 + HCl
+  N2 +
[CH 3CH 2CH 2CH 2 N N:Cl ] CH 3CH 2CH 2CH 2
1-butanediazonium chloride (a carbocation)

(a diazonium salt)
(highly unstable)
This carbocation yields a complex mixture of various products about which you
studied in sub-Sec.11.5.5.
Similarly, diazotisation of primary aromatic amines leads to aryl diazonium

96 salts or arenediazonium salts. Arenediazonium salts are more stable than
alkyldiazonium salts and can be stored at temperatures between 273 K and

278 K. Arenediazonium ions undergo a variety of reactions and are versatile
intermediates in the synthesis of a variety of aromatic compounds about which
you will study in detail in the next section. The formation of an arenediazonium
salt can be represented as shown below:
+ 
Ar NH 2 + 2 NaNO 2 + 2 HX Ar N N:X + NaX + 2 H 2O
primary arenediazonium salt

aryl amine (stable below 278 K)
SAQ 1
Why are aryl diazonium salts more stable than alkyl diazonium salts?
12.3 REACTIONS OF DIAZONIUM SALTS

You have studied the formation of diazonium salts in the last section. It has
been pointed out that arenediazonium salts are stable at temperatures below
278 K and can be used in the synthesis of aromatic compounds. You will now
study various reactions undergone by arenediazonium salts.
12.3.1 Conversion to Phenols–Reaction with Water

The most general method for the preparation of phenols involves the heating
of the diazonium salt in aqueous acid.
+ 
NH2 N2 HSO4 OH
1. H2SO4, NaNO2 H2SO4, H2O

1. 2.
2. H2O 373 K
Br Br Br
3-bromobenzennamine 3-bromobenzenol
(m-bromoaniline) 3-bromophenol
(m-bromophenol)
(78%)
12.3.2 Conversion to Benzene-Replacement of

Diazonium Group by Hydrogen
When a diazonium salt is treated with hypophosphorous acid, H3PO2, the
diazonium group is replaced by hydrogen. Reactions of this type are called
reductive deaminations.
This reaction is useful when we introduce an amino group into an aromatic

ring to influence the orientation of a subsequent reaction. Later the amino
group can beremoved by converting it into the diazonium salt and then treating
97
the diazonium salt with H3PO2. For example, direct bromination of benzene
leads to 1,2,3- and 1,2,4-tribromobenzenes.
Br Br Br
Br
Br2 Fe/FeBr3
+
FeBr3
benzene bromobenzene 1,2-dibromobenzene Br

1,4-dibromobenzene
Br2/FeBr3 Br
Br
Br
Br
+
Br
1,2,3-tribromobenzene Br
1,2,4-tribromobenzene
Thus, 1,3,5-tribromobenzene which cannot be prepared by direct bromination

of benzene can be obtained by the reaction of the diazonium salt of
tribromoaniline with H3PO2.
NH2
N 2 Cl 
Br Br
Br Br Br Br
NaNO 2,HCl H3PO2
H2 O
Br
Br Br
2,4,6-tribromoaniline diazonium salt 1,3,5-tribromoaniline
SAQ 2
How will you convert 4-methylbenzenamine to toluene?
12.3.3 The Sandmeyer Reaction

The reactions of diazonium salts involving cuprous salts are called
Sandmeyer reactions. Arenediazonium salts react with cuprous chloride,
cuprous bromide and cuprous cyanide to give products in which the diazonium
group has been replaced by Cl, Br and CN groups, respectively.
+ 
NH2 N2 Cl Cl
NaNO2, aq. HCl CuCl,HCl + N2

298 K 273-298 K
CH3 CH3 CH3
p-chloroaniline p-chlorotoluene
(70-79%)
98
+ 
NH2 N2 Br Br
Cl Cl Cl
NaNO2, aq. HBr CuBr
+ N2
283 K HBr
o-chloroaniline (89-95%)
o-bromochlorobenzene
NH 2 N2+Cl CN
Cl Cl Cl
HCl/NaNO2 CuCN
+ N2
263-273 K
o-chlorobenzenamine o-chlorobenzonitrile
(65% overall)
Reactions similar to the Sandmeyer reactions may be accomplished by the

use of copper powder as a catalyst for decomposing the diazonium salt. This
method is particularly useful in cases where the corresponding cuprous salt
cannot be prepared. This variation is called the Gattermann reaction.
+  NaNO2, Cu
Ar&N2X Ar&NO 2
+ SO2, H2O
Ar&N2X
 Ar&SO 2H
Cu sulphinic acid
+  KNCO, Cu
Ar&N2X Ar&N=C=O
aryl isocyanate
12.3.4 Formation of Aryl Fluorides

The diazotisation of an amine with sodium nitrite and fluoboric acid, HBF4,
yields diazonium fluoborate salt as a precipitate which is isolated and
decomposed thermally to yield aryl fluorides. This reaction is also known as
Schiemann reaction.
+ +
NH2 N2 BF4 F
NaNO2

aq. HBF4, 273 K + N2 + BF3
CH3 CH3 CH3
3-methylbenzenamine 3-methylbenzenediazonium 3-methylfluo-

(m-toluidine) fluoborate orobenzene
(m-methylbenzenediazonium (m-fluorotoluene)
fluoborate)
(76-84%)
12.3.5 With Potassium Iodide

Diazonium salts react with potassium iodide to yield aryl iodides. The
diazonium salt is prepared in the usual way and a solution of potassium iodide
is then added to the reaction mixture which is heated to yield the aryl iodide. 99
NH2 I
Br Br
1. NaNO2, HCl, H2O, 273 K
2. Kl
2-bromobenzenamine 2-bromoiodobenzene
(o-bromoaniline) (o-bromoiodobenzene)
(72-83%)
SAQ 3
Give reagents used in the following reactions of benzenediazonium salt to give
the products shown below:
i) Nitrobenzene
ii) Phenol
iii) Chlorobenzene
iv) Iodobenzene
12.3.6 Arylation
Basic solutions of diazonium salts react with aromatic compounds in cold to
yield biaryl compounds in which the diazonium group has been replaced by an
aromatic ring. This is illustrated by the following example.
+ _
NH2 N2 Cl
1. NaNO2 2. NaOH
CH 3
aq. HCl benzene, 278 K
CH3 CH3 4-methylbiphenyl

(21%)
4-methylbenzenamine a diazonium salt
This reaction is called the Gomberg-Bachmann reaction.
12.3.7 Conversion to Azo Dyes: Coupling Reactions

Arenediazonium salts are weak electrophiles and attack aromatic ring of highly
activated compounds such as amines and phenols to yield azo compounds.
This electrophilic aromatic substitution reaction is called diazo coupling and

is shown below:
Coupling takes place
preferably at the para
273 K
position, if it is free. If + 
N2 Cl  + OH N N OH
it is not, then, the NaOH, H2O
coupling takes place
at the ortho position.
benezenediazonium benzenol 4-hydroxyazobenzene
chloride (phenol) (orange)
100
+ 
N2 Cl  + N(CH 3)2 N N N(CH 3)2
benezenediazonium N,N-dimethylbenzenenamine 4-(N,N-dimethyl)aminoazobenzene

chloride (butter yellow)
The azo compounds thus obtained are highly coloured and many of them are
used as colouring agents and are called azo dyes. Butter yellow was once
used as a food colouring agent.
Azo dyes are also used as indicators and for textile dying. Some examples are
given below:
N(CH 3)2
 +
N N SO 3 Na
OH
N
Orange II
N
(an industrial dye
for testiles)
 +
SO 3 Na  +
SO 3 Na
 +
SO 3 Na
methyl orange
(an indicator) N N N N
NH2 NH2
(red at pH = 3.1
yellow at pH = 4.4) Congo red
(blue-violet at pH = 3
red at pH = 5)
After studying the reactions of diazonium salts, answer the following SAQ.
SAQ 4
Write the starting materials required for the preparation of azo compounds
methyl orange and Congo red.
Let us now summarise what we have learnt in this unit.
12.4 SUMMARY
In this unit, you have studied that
 Amines undergo nitrosation reaction with nitrous acid which gives

various products depending upon whether the amine is primary,
secondary or tertiary and is aliphatic or aromatic.
 The diazonium salts can be prepared by the reaction of primary amines

with nitrous acid.
101
 Diazonium salts can be used to synthesise a variety of aromatic

compounds and azo dyes.
 The reactions of diazonium salts can be summarised as follows:
4-chloro-1-methylbenzene
Cl
OH Br
CH3
CH3 CuCl, 363 K CuBr, CH3
HCl HBr
4-methylbenzenenol H2O 4-bromo-1-methylbenzene
373 K
+ -
NH2 N2 HSO4 I
H2SO4, NaNO2, H2O KI

273-278 K (no catalyst necessary)
CH3 CH3 CH3

CuCN 4-iodo-1-methylbenzene
4-methylbenzenamine 4-methylbenzenediazonium
(para-toluidine) hydrogen sulphate CN
(not isolated)
NaNO2
hypophophorous
acid, H3PO2 NO 2
CH3
4-cyano-1-methylbenzene
CH3
4-nitro-1-methylbenzene
CH3

1. Write the product of nitrosation of the following compound:
NH2
2. Why is it recommended to keep to temperature low while carrying out the

diazotisation reaction?
3. How will you carry out the following conversions?
a) 4-bromoaniline to 4-bromophenol
b) 3- chlorobenzenamine to 3- chlorofluorobenzene
102
4. Identify A, B, C and D in the following reactions:
i) NH2
NO2
HCl/NaNO2 CuCN
A B + N2
263-273 K
ii) NH2
1. NaNO2 2. NaOH
C D
aq. HCl toluene, 278 K
CH3
4-methylbenzenamine
5. How will you synthesise 2-bromoiodobenzene using a diazotisation

reaction?
12.6 ANSWERS
Self-Assessment Questions
1. Resonance structures are possible for aryl diazonium ion in which the
positive charge is delocalised in the aromatic ring; this increases its
stability as compared to the alkyl diazonium ion in which such resonance
stabilisation is not possible
2. By first converting it to diazonium salt by diazotisation reaction and then

treating the diazonium salt with hypophosphorous acid.
3. i) Copper powder, NaNO2
ii) Water
iii) CuCl/HCl
iv) KI
4. For Methyl orange:
NH2 N(CH 3)2
and
 +
SO 3 Na
 +
For Congo red SO 3 Na
H2N NH2 and 2 equivalents of
NH2
103
Terminal Questions
+ 
1. N2 Cl
2. Because at higher temperatures, the water present will react with the
diazonium salt and lead to formation of phenols.
+ -
3. a) NH2 N2 HSO4 OH
1. H2SO4, NaNO2 H2SO4, H2O

1. 2.
2. H2O 373 K
Br Br Br
4-bromobenzenamine 4-bromobenzenol
(p-bromoaniline) 4-bromophenol
(p-bromoaniline)
+ +
b) NH2 N2 BF 4 F
NaNO2

aq. HBF4, 273 K + N2 + BF3
Cl Cl Cl
3-chlorobenzenamine 3-chlorobenzenediazonium 3-chlorofluorobenzene

fluoborate
(m-chlorobenzenediazonium
fluoborate)
A is B is
4. i)
+ &
N2 Cl CN
NO 2 NO 2
and
ii) C is D is
+ 
N2 Cl
CH3 N N CH3
CH3
5. Starting with 2-bromobenzenamine and converting it to the diazonium

salt. This is followed by the reaction of the diazonium salt obtained with
KI.
NH2 I
Br 1.NaNO2,HCl,H2O,273 K Br
2.KI
2&bromoaniline 2&bromoiodobenzene
104

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Unit 9 Carboxylic Acid

Expected Learning Outcomes

 predict and correlate the physical properties such as melting point,

 list various methods of preparation of carboxylic acids;

 outline the synthesis of various carboxylic acids using the above

 explain various reactions of carboxylic acids; and

 describe the importance and uses of carboxylic acids.

9.2 STRUCTURE AND REACTIVITY

Table 9.1: Some Carboxylic Acids

Structure IUPAC Name Common Name

OH 2-Hydroxypropanoic acid Lactic acid

HOOC – COOH Ethanedioic acid Oxalic acid

HOOC(CH2)4COOH Hexanedioic acid Adipic acid

CH2=CH-COOH Propenoic acid Acrylic acid

OH 2,3-Dihydroxybutanedioic acid Tartaric acid

The carboxylate ion can be represented as a resonance hybrid of the following

The reaction with ..

Even 5% sodium bicarbonate (NaHCO3) solution is basic enough (pH = 8.5) to

Such a protonation or basicity plays an important role in many reactions of the

9.3 PHYSICAL PROPERTIES OF MONO-

Table 9.2: Physical Properties of Carboxylic Acids

Methanoic acid 281 374 

Ethanoic acid 289 391 

Propanoic acid 252 414 

Butanoic acid 268 437 

Pentanoic acid 239 459 4.97

Hexanoic acid 270 478 0.968

Heptanoic acid 265 496 0.244

Octanoic acid 290 512 0.068

Nonanoic acid 288 528 0.026

Decanoic acid 305 543 0.015

Benzenecarboxylic 395 522 0.21

Fig. 9.1: Saw-tooth pattern of melting points.

dimer of ethanoic acid in vapour phase

Let us now study how monocarboxylic acids are prepared.

9.4 PREPARATION OF MONOCARBOXYLIC

Table 9.3: Some Methods of Preparation for Carboxylic Acids

2. Side-Chain Oxidation of Alkylbenezenes

3. Oxidation of Primary Alcohols

5. Oxidation of Methyl Ketones (Haloform reaction)

Note that the alkyl benzenecarboxylic acid

3. Oxidation of Primary Alcohols

1900 and for which .. .. ..  +

Grignard reagents CH3 CH3

phenyllithium benzenecarboxylic acid

Primary and secondary alkyl halides may be converted to carboxylic acids

This method is complementary to carbonation of organometallic reagents as

ii) Hexanoic acid

iii) 4-Methylbenezenecarboxylic acid

9.5 REACTIONS OF CARBOXYLIC ACIDS

Table 9.4: Reactions of Carboxylic Acids

RCOOH + CH2N2 RCOCH3 + N2 (by diazomethane)

3. Conversion to 2-halo acids

6. Conversion to alkanoyl halides

RCOOH + SOCl2 RCOCl + SO2 + HCl

RCOOH + PCl3 3 RCOCl + H3PO3

RCOOH + PCl5 3 RCOCl + POCl3 + HCl

Before studying the mechanism of acid-catalysed esterification, it is interesting

Step 1: Protonation of the carboxy group

Step 3: Elimination of water and deprotonation

Tertiary alcohols and phenols cannot be used in acid catalysed esterification.

.. of choice for the