Esterification

October 27 28, 2011

Esters
Volatile esters typically smell fruity

Fischer esterification

Conversion of a carboxylic acid and an alcohol to an

ester under acid catalysis
This is a condensation reaction- 2 molecules make one
molecule, and a small molecule is lost (H2O)
Reaction is in equilibrium and does not go to completion

Mechanism

Isolation flowchart
Benzoic acid
Methanol
Methyl benzoate
Sulfuric acid

1. Reflux
2. Cool and dilute with
CH2Cl2
3. Extract with H2O

Benzoic acid
Methyl benzoate

Methanol
Sulfuric acid

CH2Cl2

H2O

Extract with NaHCO3

Methyl benzoate

Sodium benzoate

CH2Cl2

H2O

HCl

Benzoic acid
H2O

Purification of product and

starting material
Benzoic acid
1.
2.
3.
4.

Vacuum filter
Wash with cold water
Air dry
Obtain mass and MP

Methyl benzoate
1.
2.
3.
4.
5.

Dry over MgSO4

Gravity filter
Evaporate solvent
Distill
Obtain mass

The entire procedure must be finished in one lab session

Be well organized

Multiple ways to define yield

Percent yield

Percent conversion - a measure of how much starting material was

consumed regardless of whether it was destroyed or converted to
product or side product

Process yield - a measure of how much of the starting material became

desired product [yield corrected for recovered starting material]

Equilibrium constant

At the end of the reaction, you will recover both methyl benzoate and
benzoic acid to determine Keq
How can we drive the reaction forward? Le Chateliers principle.

Keq calculation
You will determine Keq (equilibrium constant) 2 ways
based on benzoic acid consumed
based on methyl benzoate created
Benzoic
acid

Methanol

Methyl
benzoate

Water

Initial

Bi

Mi

Change

-x

-x

+x

+x

equilibrium

Bi - x

Mi - x

Keq based on
methyl benzoate
recovered
Assume Bf = moles of benzoic acid at equilibrium, so Bf = Bi x and x = Bi Bf
Substitution gives:
Note: because all 4
Keq based on benzoic components are in the same
volume, you can use moles
acid recovered
rather than concentration

Some Helpful Tips

Interpreting Esterification 1H NMR Spectra:
For the starting material, the peak at 10.9 ppm
can be considered as integrating to 1
broad peaks often have low integration values
For the product, the peak at 3.898 ppm integrates
to 3 (in case youre using an old version of the
lab manual)

More NMR examples