Ester

Learning Outcome:
Draw the structural formula of the ester that could be produced by
the condensation reaction between an alcohol and a carboxylic acid,
given their structural formulae, and write an equation for the
reaction.

Give systematic name for the ester formed

Identify, draw structures and name the alcohol and acid (or
carboxylate salt) that could be obtained by hydrolysis of an ester,
given its structural formula.

Explain the use of heating under reflux and the presence of a trace
of concentrated sulfuric acid in the laboratory production of ester.

Explain the steps involved in isolating pure ester.

Ester
General formula of esters is
C
n
H
2n+1
COOC
m
H
2m+1
. (R-COO-R)

Ester is obtained by combining the general
formulae of carboxylic acids and alcohols.

The functional group of an
ester is carboxylate group COO
-
General Esterification
RCOOH + ROH RCOOR + H
2
O

Ester is prepared through esterification,
using concentrated sulfuric acid under
reflux method.
Nomenclature of Esters
Name the alcohol part (replace anol with yl)
followed by carboxylic acid part (replace ic with
ate). Number(s) in the parent alcohol &
carboxylic acid is retained.

Example :
HCOOH + CH
3
OH HCOOCH
3
+ H
2
O
Methanoic methanol Methyl methanoate
acid
Types of esters :





2-methyl-1-prophyl ethanoate
2-propyl butanoate
2-propyl-2-ethylbutanoate
Isomer
Same molecular formula but
different structural formula
Classification Carboxylic acid
CH
2
CH
3
-COOH
Ester
CH
3
-COO-CH
3
Functional group
Physical properties
Chemical properties
Very polar carboxyl group polar ester group
Strong H-bonds between
molecules
Non-valotile liquid at r.t.p
Higher MP/BP
Very soluble in water
Weak DDI between
molecules
Gas at r.t.p
Lower MP/BP
Insoluble in water
Acidic, neutralisation
react with alcohols
condense to ester
Fairly unreactive
Hydrolysed to acid
and alcohol
Physical Properties
State at room temperature pressure (r.t.p)

Ester are volaitle liquid at r.t.p compare to its isomeric
acid (carboxylic acid) with same molecular mass
Why?
Ester has a polar ester group
Molecules held together loosely by
weak DDI
HE at r.t.p easily break the weak DDI
Carboxylic acid has a very
polar carboxyl group
Held together by stronger
H-bond
HE at r.t.p cannot break the
strong H-bond

Physical Properties
O
- Melting and
Boiling Point
- C
+ bp
= 126
o
C range = 120-125
o
C
O
-
Moderate lower than ROH
and RCOOH
higher than
alkane and alkene
- Polar ester functional group, ester
molecules can form intermolecular dipole-
dipole interactions.
DDI
Solubility in water





Solubility in water is low.
small molecular mass ester group are soluble in water.
Has a polar ester group, can form hydrogen bond with
very polar water molecules, but not extensive (blocked
by the non-polar parts)
Solubility decreases when carbon chain length increase.

Hydrogen bond
Blocked by
non-polar
HC chain
Odour
Sweet and fruity smell

Example :
Allyl hexanoate (pineapple)
Benzyl acetate( pear, strawberry, jasmine)

Steric Factors







Larger alkyl group (non polar hydrocarbon) hamper the
reactivity of the functional group, making it less reactive.
Less steric factors more reactive
This apply to all organic compounds with functional
groups.
Less steric
More reactive
Preparation of esters
Preparation of esters
An ester is prepared by reacting, under
reflux, an alcohol with a carboxylic acid in
the presence of concentrated sulfuric acid
as a catalyst.
The ester forming (process) reactions are
called esterifications.
Water is produced in this (type) reaction
condensation
H
+

ROH + HO C R RO C R + H
2
O
|| Reflux ||
O O
Alcohol Carboxylic Ester Water
acid

Acid loses a OH group and alcohol loses a proton. A
molecule of water is eliminated.

This reaction is reversible, attain equilibrium.

Concentrated H
2
SO
4
used only a trace as catalyst.
H
2
SO
4
is a dehydrating agent. It removes water causing
the equilibrium to move to the right and thus increase the
yield of ester.

Complete the following reactions:
Draw the alcohol and carboxylic acid used
to synthesizes the ester below:
Esterification

1.Reflux
heat mixture in a vessel with a water-cooled
condenser to prevent loss of volatile material

2. Separation
-separating funnel to separate organic layer from
aqueous layer

3. Purification
distillation to obtain pure ester
1. Reflux
Refluxing is a process of repeating vapourisation
and condensation of organic substances to
prepare organic compounds by heating the
mixture in reflux setup.
Purpose
increase the rate of reaction (by heating)
- to prevent the loss of volatile organic
compounds (by condenser).
Species present after reflux- Ester, H
2
O, ROH,
RCOOH and H
2
SO
4
.

Reflux method
2. Separation
Transfer the cooled reaction mixture into a
separating funnel.
Purpose
To separate 2 immiscible layers
Add some distilled water to remove water
soluble compound- ROH, RCOOH and H
2
SO
4
.
Stopper, shake, release the gases formed
Place it back to retort stand, remove the stopper
and allow it to separate into 2 layers.
Remove the aqueous layer.
Add some Na
2
CO
3
(aq) to remove acids
such as H
2
SO
4
and RCOOH by converting
them into more water soluble form.
Transfer the clean ester to conical flask.
Add anhydrous calcium chloride to absorb
excess water.
Equation?
3. Purification
Purpose
Distill it to obtain pure ester.
Record the boiling range, odour and
appearance.
Question
The following structures of two synthetic
flavour compounds. For each compound:

a) Draw the structures of the carboxylic acid and
alcohol from which they could be prepared.
O CH
2
CH
3
|| |
CH
3
C O CH
2
CHCH
2
CH
3
O
||
CH
3
CHCH
2
C O CH
2
CH
2
CH
2
CH
3
|
CH
3


Carboxylic acid Alcohol
b) Write an equation for the esterification
reaction.
O CH
2
CH
3
|| |
CH
3
C O CH
2
CHCH
2
CH
3


O
||
CH
3
CHCH
2
C O CH
2
CH
2
CH
2
CH
3
|
CH
3


Hydrolysis of Esters
Hydrolysis of esters
Esters undergo hydrolysis when refluxed with
aqueous acid or base.
Hydrolysis is a chemical reaction where the
splitting of a molecule is accompanied by the
addition of water molecule.
In the hydrolysis of ester the H appears on the
alcohol and the OH on carboxylic acid.
Ester broken down to its carboxylic acid and
alcohol.
Hydrolysis of Ester
Acid catalysed hydrolysis of ester

RCOOR + H
2
O RCOOH + ROH
Reflux
O
||
CH
3
CH
2
O C CH
3
+ H
2
O
O
||
CH
3
CH
2
OH + CH
3
-C - OH
Alkaline hydrolysis of ester
(similar to saponification)

RCOOR + OH
-
RCOO
-
+ ROH
Carboxylate salt alcohol
RCOO
-
(aq) + H
+
(aq) RCOOH (aq/l/s)


This method is preferred because the acid is
removed from the equilibrium as its salt.
This drives the equilibrium to the right and so
alkaline hydrolysis is essentially irreversible,
giving a higher yield of products.

O O
|| + NaOH || + HOR
R C OR R C O
-
Na
+

To obtain the acid from the salt, hydrogen
ions are required, in the form of dilute
mineral acid
O O
|| + HCl
(aq)
|| + NaCl
(aq)
R-C O
-
Na
+
R- C OH



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