Esterifiication

Dr. G. Madhumitha
Organic Chemistry Division,
SAS

Introduction
Formed when an alcohol reacts with a acid.
Very slow reaction, unless! an acid catalyst used
(usually sulphuric acid)

A condensation reaction
The condensation reaction between the hydroxyl
group and the carboxylic acid
esterification.
Reverse reaction = ester hydrolysis

known

as

Names of esters
end in oate.

Naming

Named after alcohol & acid from which they

are derived.
O

C
CH3

CH2

CH3

lets name
some esters!

ethyl

this part comes from the

alcohol & is named after it

ethanoate

this part from the acid

and is named after it

Structural formulae
Although the previous structural formula are the clearest
way of showing esters, they can draw out in a
shortened form.
In this version
ethyl ethanoate
O

Either
CH3 CH2

CH3

Or

CH3 C

the acid part

has been
written first

CH2

CH3

Identify the group attached to the C=O this is from

the acid
The group attached to the O- is from the alcohol.

ester
ethyl methanoate
3-methylbutyl ethanoate
ethyl 2-methylbutanoate
phenylmethyl ethanoate

fragrance
raspberries
pears
apples
jasmine

Esters have strong, sweet smells.

Their bouquet is often floral or fruity.
This means they are used in food flavourings &
perfumes.
Also, very good at dissolving organic compounds so
often used as solvents.

Esterification by organic acids

An ester is defined as a compounds formed by
substituting an orgaic radical for an ionizable
hydrogen of an acid
In direct esterification, eg. Acetic acid by alcohol
(ethanol), the possibility is there in breaking the C=O
bond or alkyl oxygen bond.

The evidence for the breaking of carbonyl oxygen bond

was found by the following rxn.

If the alkyl sulfur bond had broken, hydrogen sulfide would have formed.

Berthelot and Pean de St Gilles made the first measurement on the acetic acid
ethanol equilibrium and determined the equilibrium point.
The results showed that the reaction was reversible and depends on the amount of
compound present.

The equilibrium constant for the reaction is

[Ester X water] / [Acid X Alcohol] = K
Menschutkin has done extensive work on the equilibrium constant of large numbers
of acids and alcohols. (Tabulation 12-I, Pg 697)
It was observed that methyl showed the greatest initial rate of esterification
The primary alcohols such as ethyl, propyl and butyl same initial values
The secondary alcohol showed lower than primary alcohol
In case of tertiary alcohol, the limit is very less, since they get dehydrated very
easily to unsaturated hydrocarbons.
Formic acid reacts much faster than other branched- chain acids.

 The trimethylacetic acid dimetylethyl acetic acid are relatively slow.

Maleic acid is esterified 14 times as rapidly as fumaric acid
The esterification of unsaturated acids such as cinnamic and sorbic
starts very slowly that corresponding saturated acids but goes in
faster rate.
The purely aromatic acids such as benzoic, p-toluic esterfies very
slowly.

Esterification of carboxylic acid derivatives Alcoholysis

In the alcoholysis or ester interchange rxn, an alcohol reacts with an
ester to give new ester
If a mixture of amyl nitrite and ethyl alcohol containing an acid catalyst
is warmed- ethyl nitrite distils out.
Friedal crafts heated ethyl acetate with amyl alcohol and amyl acetate
with ethyl alcohol and observed alcoholysis occurs.
They also heated ethyl benzoate and amyl acetate together and
obtained ethyl acetate and amyl benzoate though the reaction was
slow below 300 C.

Completing Alcoholysis:
The removal of one reactant makes the reaction to complete.
When higher alcohols were heated in fractionating column, the volatile
constituents distils off.

Utilization of Alcoholysis
Preparation of monomeric cyclic polymethylene
carbonates
Higher polymethylene glycol and sodium are heated
with butyl carbonates to obtain polymeric polymethylene
carbonate
EQUIPMENT & OPERATION FOR ALCOHOLYSIS

Corrosion resistant usage of anhydrous esters, alcohols

Batch Process Kettle and Column
Kettle alcohol + Sodium
Later Ester run then heated
Volatile component distils off

Esterification by addition of unsaturated systems

Addition of an acid to Olefin

Esters from Acetylene
Esterification by ketene
Esterification by ethylene oxide
Esters from Carbon Monoxide

Addition of an acid to Olefin

Addition of organic acid to an unsaturated hydrocarbon
in the presence of strong acid
The addition of carboxylic acids to the double bonds of
isobutylene and trimethylethylene gives tertiary esters.
Formic acid to olefins is easily controlled and gives high
yields of esters.
Optimum condition for the esterification of olefins by
carboxylic acids require low reaction temperature, high
concentrations of reactants and anhydrous conditions

Esters from Acetylene

Acetylene and acetic acid vinyl ester or ester of
ethylidene diacetate formed
Vinyl acetate used for polymer preparation
Ethylidene diacetate acetic anhydride synthesis
Zinc acetate widely used in vinyl acetate preparation
200 C or above
Strong acids as catalyst

Esters from ketene

Ketene + alcohol esters
No by products

Salicylic acid can be acetylated by ketene

BF3 is an excellent catalyst

Esters from ethylene oxide

Ethylene oxide reacts with water to form glycol

Ethylene oxide reacts with alcohol to give glycol ether

With acetic acid to give glycol acetates
Esterification is done by passing ethylene oxide into heated
acid containing sulphuric acid/ catalyst
Above 150 C, under pressure, in the presence of catalyst,
ethylene oxide and carbon dioxide combine to give ethylene
carbonate

Esters from Carbon monoxide

Carbon monoxide with an alcohol at elevated temperature

and high pressure in the presence of metal alkoxide gives

alkyl formate