CARBOXYLIC ACIDS

Introduction, nomenclature, examples of aliphatic carboxylic acids

Organic compounds that contain one or more carboxyl groups, (-COOH) have acidic properties and are
known as carboxylic acids.
The word carboxyl rightly represents this functional group in the sense that it is a combination of the carbonyl
group and the hydroxyl group as shown below:

They may be considered as carboxyl derivatives of hydrocarbons where one or more hydrogen atoms are
replaced by carboxyl groups.
Acids containing one carboxyl group are called monocarboxylic acid and those with two or three carboxyl
groups are called di- and tri- carboxylic acids respectively.
Introduction of carboxylic acids - Replacement of hydroxyl group in carboxylic acids with a halogen,
carboxylate, alkoxy or amino group gives functional derivatives of carboxylic acid known as acyl halides, acid
anhydrides, esters or amides respectively.

Nomenclature of carboxylic acids

Since carboxylic acids are amongst the earliest organic compounds to be isolated from nature, a large
number of them are known by their common names.
The common names end with the suffix-ic acid and have been derived from Latin or Greek names of their
natural sources.

For e.g., formic acid (HCOOH) was first obtained from red ants (formica means ant),
acetic and (CH3COOH) from vinegar (acetum means vinegar)
butyric acid (CH3CH2CH2COOH) from rancid butter (butyrum means butter)
caproic acid (CH3CH2CH2CH2COOH) from goats (caper means goat).

The positions of the substitutes are indicated by Greek letters a, b, g,d etc the a-carbon being the one directly
attached to the carboxyl group, b - the next and so on.
In the IUPAC system, the monocarboxylic acids are named as alkanoic acids. The name of the acid is
derived by replacing the terminal 'e-' of the corresponding alkane with '-oic acid'. Carboxyl carbon is always
given number one while numbering the carbon atoms of the parent chain.
Examples:

Structure of carboxylic group

Electron and neutron diffraction studies show that carboxyl group has a planar structure.

Thus the carboxylic carbon and the two oxygen atoms in carboxylic group are sp2 hybridized. The carboxylic
carbon forms are (sp2 - sp2) s - bond with two oxygen atoms.
One the oxygen atoms form (sp2 - s) s - bond with a hydrogen atom. One half filled unhybridized p-orbital of
the carbon and the unhybridized p-orbital of the oxygen atom undergo sideways overlap.

This results in the formation of the delocalized p-electron cloud. This is confirmed by the C-O single bond
length in formic acid being shorter than the C-O bond length in ethanol.

The carboxyl group has the following resonating structures.

The third resonance structure (C) has all atoms with their full quota of electrons (closed shell structure) and
thus is more stable and more important contribution to the resonance hybrid than the second structure (B) in
which the positively charged carbon atom has only six electrons in its valence shell (open shell structure).

This in two important resonance structures [A] and [C] the carboxyl carbon is electrically neutral.The carboxyl
group is also polar due to resonance structures [B] and [C].
In aldehydes and ketones, only one structure is electrically neutral. As a result, the carboxyl carbon of the
resonance hybrid, in acids, is less positive and less electrophilic than the carbonyl carbon of aldehydes and
ketones.

Preparation of monocarboxylic acids

1. From primary alcohols and aldehydes
Primary alcohols are readily oxidised to carboxylic acids with common oxidising agents such as potassium
permanganate (KMnO4) in neutral, acidic or alkaline media.

The acid is first obtained as its potassium salt, which on treatment with mineral acid gives the carboxylic
acid.Oxidation with K2Cr2O7 or CrO3 in acidic media often gives some amount of esters. Hence the oxidation
by KMnO4 is preferred.
Readily available aldehydes can also be used to obtain carboxylic acids, which may be oxidised even by
milder oxidising agents as we have seen earlier.

2. From alkyl benzenes and alkenes- Aromatic carboxylic acids can be prepared by vigorous oxidation of
alkyl benzenes with chromic acid or acidic or alkaline KMnO4. The entire side chain, irrespective of its length,
is oxidised to the carboxyl group.

However if the benzylic carbon is tertiary, oxidation does not occur. Suitably substituted alkenes are also
oxidised to carboxylic acids with these oxidising agents.

3. From nitriles and amides

Nitriles are hydrolysed to amides and then to acids in the presence of H+ or OH − as catalyst. Mild reaction
conditions are used to stop the reaction at the amide stage.

4. From Grignard reagents

Grignard reagents react with carbon dioxide (dry ice) to form salts of carboxylic acids which in turn give
corresponding carboxylic acids after acidification with mineral acid.

As we know, the Grignard reagents and nitriles can be prepared from alkyl halides .
The above methods (3 and 4) are useful for converting alkyl halides into corresponding carboxylic acids
having one carbon atom more than that present in alkyl halides (ascending the series)

From esters
Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives carboxylates, which on
acidification give corresponding carboxylic acids.

Hydrolysis of trihalides - By the hydrolysis of trihalides containing three halogen atoms attached to the
same carbon atom, carboxylic acids are formed.

Koch Reaction
Alkenes react with CO and H2O to give C-acids in presence of H3PO4 at 573-673 K under pressure.
From Sodium Alkoxide
Its reaction with CO in presence of HCl gives C-acids.

From acyl halides and anhydrides

Acid chlorides when hydrolysed with water give carboxylic acids or more readily hydrolysed with aqueous
base to give carboxylate ions which on acidification provide corresponding carboxylic acids.
Anhydrides on the other hand are hydrolysed to corresponding acid(s) with water.

Haloform Reaction of Methyl Ketones

Although this reaction is used mainly for structure elucidation, it has synthetic utility when methyl ketones are
readily prepared and halides are not.

Properties
1. Lower members are pleasant smelling liquids with higher boiling points. The higher members are waxy
solids. Carboxylic acids are higher boiling liquids than aldehydes, ketones and even alcohols of comparable
molecular masses.
The higher boiling points are explained
on the basis of association
by hydrogen bonding.

2. The first few members are highly soluble in water and higher members are insoluble. This can also be
explained on the basis of hydrogen bonding between acids and water. With higher members the size of the
alkyl group is increased which repels the hydrophilic groups.
3. The M.Pts of C-acids show alteration effect.
The acids having even no. of c-atoms have high M.Pt as compared to acids having odd no of C-atoms.

Chemical Reactions
Reactions Involving Cleavage of O–H Bond are

Acidity - Reactions with metals and alkalies The carboxylic acids like alcohols evolve hydrogen with
electropositive metals and form salts with alkalies similar to phenols.
However, unlike phenols they react with weaker bases such as carbonates and hydrogencarbonates to
evolve carbon dioxide.
This reaction is used to detect the presence of carboxyl group in an organic compound.

Carboxylic acids dissociate in water to give resonance stabilised carboxylate anions and hydronium ion.

For the above reaction

where Keq, is equilibrium constant and Ka is the acid dissociation constant.

For convenience, the strength of an acid is generally indicated by its pKa value rather than its Ka value.
pKa = – log Ka
Smaller the pKa, the stronger the acid ( the better it is as a proton donor).
Strong acids have pKa values < 1, the acids with pKa values between 1 and 5 are considered to be
moderately strong acids,
weak acids have pKa values between 5 and 15, and extremely weak acids have pKa values >15.

Carboxylic acids are weaker than mineral acids, but they are stronger acids than alcohols and many simple
phenols (pKa is ~16 for ethanol and 10 for phenol).
In fact, carboxylic acids are amongst the most acidic organic compounds you have studied so far.
You already know why phenols are more acidic than alcohols. The higher acidity of carboxylic acids as
compared to phenols can be understood similarly.

The conjugate base of carboxylic acid, a carboxylate ion, is stabilised by two equivalent resonance
structures in which the negative charge is at the more electronegative oxygen atom.
The conjugate base of phenol, a phenoxide ion, has non-equivalent resonance structures in which the
negative charge is at the less electronegative carbon atom.
Therefore, resonance in phenoxide ion is not as important as it is in carboxylate ion.

Further, the negative charge is delocalised over two electronegative oxygen atoms in carboxylate ion
whereas it is less effectively delocalised over one oxygen atom and less electronegative carbon atoms in
phenoxide ion.
Thus, the carboxylate ion is more stabilised than phenoxide ion, so carboxylic acids are more acidic
than phenols.

Effect of substituents on the acidity of carboxylic acids:

Substituents may affect the stability of the conjugate base and thus, also affect the acidity of the carboxylic
acids.
Electron withdrawing groups increase the acidity of carboxylic acids by stabilising the conjugate base
through delocalisation of the negative charge by inductive and/or resonance effects.
Conversely, electron donating groups decrease the acidity by destabilising the conjugate base.

The effect of the following groups in increasing acidity order is

Thus, the following acids are arranged in order of decreasing acidity (based on pKa values):

Direct attachment of groups such as phenyl or vinyl to the carboxylic acid, increases the acidity of
corresponding carboxylic acid, contrary to the decrease expected due to resonance effect shown below:

This is because of greater electronegativity of sp2 hybridised carbon to which carboxyl carbon is attached.
The presence of electron withdrawing group on the phenyl of aromatic carboxylic acid increases their acidity
while electron donating groups decrease their acidity.

Reactions Involving Cleavage of O-H Bond

1. Fatty acids react with alkalies to form salt and water and liberates CO2 with carbonates (stronger than
carbonic acid).

2. They liberate hydrogen, when react with electropositive metals like zinc or magnesium.

Reactions Involving Cleavage of C–OH Bond

1. Formation of anhydride
Carboxylic acids on heating with mineral acids such as H2SO4 or with P2O5 give corresponding anhydride.

2. Esterification
Carboxylic acids are esterified with alcohols or phenols in the presence of a mineral acid such as
concentrated H2SO4 or HCl gas as a catalyst.

Mechanism of esterification
Protonation of the –OH group of the acid, enhances the nucleophilic attack by alcohol to give the ester.

Step 1. Protonation of carboxylic acid

Step 2. Attack by nucleophile and loss of proton.

3. Reactions with PCl5, PCl3 and SOCl2 - The hydroxyl group of carboxylic acids, behaves like that of
alcohols and is easily replaced by chlorine atom on treating with PCl5, PCl3 or SOCl2. Thionyl chloride (SOCl2)
is preferred because the other two products are gaseous and escape the reaction mixture making the
purification of the products easier

4. Reaction with ammonia - Carboxylic acids react with ammonia to give ammonium salt which on further
heating at high temperature give amides. For example:

Reactions Involving –COOH Group

1. Decarboxylation
Carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium salts are heated with sodalime
(NaOH and CaO in the ratio of 3 : 1). The reaction is known as decarboxylation.

Alkali metal salts of carboxylic acids also undergo decarboxylation on electrolysis of their aqueous solutions
and form hydrocarbons having twice the number of carbon atoms present in the alkyl group of the acid.
The reaction is known as Kolbe electrolysis

Hunsdiecker Reaction

The silver(I) salts of carboxylic acids react with halogens to give unstable intermediates which readily
decarboxylate thermally to yield alkyl halides.
The reaction is believed to involve homolysis of the C-C bond and a radical chain mechanism.

Dry Distillation
By the distillation of calcium salt of fatty acids with calcium formate - aldehyde is formed
This method is not suitable for preparing mixed aldehydes as shown above how ever formaldehyde can be
prepared easiely. By the distillation of calcium salt of fatty acid, ketone is formed.

Reduction
i) Carboxylic acids are reduced to primary alcohols by lithium aluminium hydride or better with diborane.
Diborane does not easily reduce functional groups such as ester, nitro, halo, etc. Sodium borohydride does
not reduce the carboxyl group.

ii) Heating with HI/P converts the carboxylic acid to alkane.

Substitution Reactions in the Hydrocarbon Part

1 . Halogenation - Carboxylic acids having an α -hydrogen are halogenated at the α -position on treatment
with chlorine or bromine in the presence of small amount of red phosphorus to give α -halocarboxylic acids.
The reaction is known as Hell-Volhard-Zelinsky reaction.

Reactions with ammonia :

Carboxylic acid reacts with NH3 to form ammonium salt which on heating undergoes dehydration to
amides, ultimately alkyl cyanide results.

Reducing property
Formic acid is unique because it contains both an aldehyde group and hydroxyl group also. Hence it can act
as a reducing agent.
It reduces Fehling’s solution, Tollens reagent and decolourises pink coloured KMnO4 solution.
In all cases formic acid is oxidised to CO2 and water.

Ring substitution
Aromatic carboxylic acids undergo electrophilic substitution reactions in which the carboxyl group acts as a
deactivating and meta-directing group.
They however, do not undergo Friedel-Crafts reaction (because the carboxyl group is deactivating and the
catalyst aluminium chloride (Lewis acid) gets bonded to the carboxyl group).

Tests for carboxylic acid

1. Aqueous solution of carboxylic acids turn blue litmus into red colour.
2. Carboxylic acids give brisk effervescence with sodium bi-carbonate due to the evolution of carbon-di-oxide.
3. On warming carboxylic acids with alcohol and concentrated sulphuric acid it forms ester which is identified
from its fruity odour.

Sulphonation :