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

CH2Cl2 Extract with NaHCO3

Methanol Sulfuric acid

H2O

Methyl benzoate
CH2Cl2

Sodium benzoate
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 Initial Change equilibrium Bi -x Bi - x Methanol Mi -x Mi - x Methyl benzoate 0 +x x Water 0 +x 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