Concept, sources, nomenclature and isomerism in alkanoate (esters).

Concept of Alkanoate: - Alkanoate (esters) are a group of organic compounds formed with an
alkyl group, R’, of an alkanol replaces the ionizable hydrogen atom in an alkanoic acid, RCOOH
to form RCOOR’, where R is H atom or an alkyl group and R’ is an alkyl. The general molecular
formula for alkanoate is CnH2nO2 where n = 2, 3, 4, 5 etc. The first member of the alkanoate
series corresponds to n = 2 and has the molecular formula C2H4O2.

When an alkanol reacts with an alkanoic acid, the products formed are ester and water only, e.g.

O O
║ + H ─ O ─ R’ ║ + H2 O
R─C─O─H R ─ C ─ O ─ R’
Alkanoic acid Alkanol Ester Water

For example, when pentan-1-ol and ethanoic acid react, pentyl ethanoate and water are produced.

H O H H H H H
| ║ | | | | |
H─C ─ C ─O ─H + H ─ O ─ C ─ C ─ C ─ C ─ C ─ H
| | | | | |
H H H H H H
Ethanoic acid Pentan-1-ol

H O H H H H H
| ║ | | | | |
H ─C ─ C ─ O ─ C ─C ─ C ─ C ─ C ─ H + H2O
| | | | | |
H H H H H H
Pentyl ethanoate Water

Esterification: - The formation of an ester by the reaction between an alkanol and an alkanoic
acid is known as esterification. This reaction is extremely slow and reversible at room
temperature, and is catalyzed by a high concentration of hydrogen ions. Simply put, esterification
is the reaction between an alkanol and alkanoic acid to produce an alkanoate/ester and water in
the presence of mineral acid as catalyst.

Esterification

Alkanol + alkanoic acid alkyl alkanoate + water.

Hydrolysis
The above reaction, that is, esterification reaction is quite analogous to the neutralization reaction
between a mineral acid and a base, which produces a salt and water only.

Acid + base salt + water

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

O
║
Ester contains R ─ C ─ O ─ R’ as their functional group, where R is hydrogen atom or alkyl
group and R’ is an alkyl group. The r and R’ may be the same or different. It also contains the
polar carbonyl group, C = O and two C ─ O single bonds attached to the same oxygen atom. All
the bonds which make up the functional group are polar. This creates four centers with partial
charge on the atoms. Charged reagents could attack at any of the points. However, the carbonyl
group is the usual site of reaction because of its strong polar nature.

Sources of alkanoate: - Animal and vegetable fats and oils are esters with high relative
molecular masses. Simple esters are present in fruits of plants and are responsible for the natural
sweet smell of flowers.

Homologous series: - The general molecular formula for alkanoate is CnH2nO2; where n = 2, 3,
4…

The first member of the alkanoate series corresponds n = 2 and has the molecular formula
C2H4O2. Its structural formula is HCOOCH3, which is called methyl methanoate. The second
member in the series corresponds to n = 3, and has the molecular formula of C3H6O2. Its
structural formula is either HCOOCH2CH3 which is called ethyl methanoate or CH3COOCH3,
which is called methyl ethanoate respectively.

IUPAC nomenclature of alkanoate (esters): - The name of an alkanoate (ester) is obtained

from the corresponding alkanol and alkanoic acid from where it is formed. The alkanol portion,
R’, is named first as alkyl; and then the link to the alkanoic acid portion, RCOO-, name as
alkanoate. In fact, from the name of an ester, it is very easy to name the alkanol and the alkanoic
acid from where it has been formed as shown below.

S/n Alkanoic acid Alkanol Formula of ester IUPAC name of ester

1. Methanoic acid Methanol HCOOCH3 Methyl methanoate

2. Ethanoic acid Methanol CH4. COOCH3 Methyl ethanoate

 3. Methanoic acid Ethanol HCOOCH2CH3 Ethyl methanoate

4. Ethanoic acid Ethanol CH3COOCH2CH3 Ethyl ethanoate

5. Propanoic acid Methanol CH3CH2COOCH3 Methyl propanoate

Estesr are named as alkyl derivatives of alkanoic acids. For example,

H O H H H
| ║ | | |
H─C ─ C ─O ─H + H ─ O ─ C ─ C ─ C ─ H
| | | |
H H H H
Ethanoic acid Propan-1-ol

H O H H H
| ║ | | |
H ─C ─ C ─ O ─ C ─C ─ C ─ H + H2O
| | | |
H H H H
Propyl ethanoate Water

When the ester, that is, propyl ethanoate is divided into two portions, the portion which does not
carry the – COO – is named as the alkyl radical. The portion which contains the – COO – is
named the carboxylate radical. Combining the two parts, our example above is named propyl
ethanoate.

The alkyl groups, R and R’, that is, of the alkanoic acid and alkanol respectively, may be the
same or different. Two other examples are:

(a) Methyl ethanoate; CH3COOCH3, and

(b) Ethyl ethanoate, CH3COOCH2CH3.
Esters are the main constitutes of many naturally occurring fats and oils. Many of them have
pleasant smells and are largely responsible for the fragrance of flowers and the flavors of fruits.
For example, pentyl ethanoate, CH3COOC5H11, has the smell of bananas and is called banana oil
while octyl ethanoate, CH3COOC8H17, has the smell of oranges.
Isomerism in alkanoate: - I. Structural isomerism: - Alkanoate with three (3) or more carbon
atoms exhibit structural isomerism, e.g.

(a) C3H6O2, represents two (2) alkanoate.

1. HCOOCH2CH3 – Ethyl methanoate; and
2. CH3COOCH3 – Methyl ethanoate.
(b) C4H8O2, represents four (4) alkanoate.
1. HCOOCH2CH2CH3 – Propyl methanoate;
2. CH3COOCH2CH3 – Ethyl ethanoate;
3. CH3CH2COOCH3 – Methyl propanoate; and
4. HCOOCH(CH3)CH3 – 2-Methyl ethyl methanoate.

II. Functional isomerism: - Every alkanoate is isomeric with one or more alkanoic acids. For
example,
(a) Methyl methanoate, HCOOCH3, is isomeric with ethanoic acid, CH3COOH; they are
functional isomers, that is, isomers that belong to different homologous series.
(b) Methyl ethanoate, CH3COOCH3, is isomeric with propanoic acid, CH3CH2COOH, both
are functional isomers.

Hence, when the molecular formula of a compound is written as CnH2nO2, it may represent an
alkanoic acid or an alkanoate. However, for an alkanoic acid, n ≥ 1 and for an alkanoate, n ≥ 2.

Difference between esterification and neutralization reaction: - The following are the major
difference between esterification and neutralization reaction.

S/n Esterification reaction Neutralization reaction

1. A carboxylic acid reacts with an An acid reacts with a base

alkanol
2. Products of reaction are alkanoate Products of reaction are salt and water.
(ester) and water.
3. Does not require an indicator Require an indicator to show end-point

4. Reaction is reversible Reaction is irreversible

5. It is acid-catalyzed It requires no catalyst

6. Molecules reacts, hence, very slow Ions reacts in a solution, hence, very
fast

7. Requires heating Heating is not required