Esterification

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Exp’t 84
Synthesis of Methyl Benzoate by Fisher Esterification
from K. L. Williamson, Macroscale and Microscale Organic Experiments, 2nd Ed. 1994, Houghton Mifflin, Boston p385 Revised 10/15/03

Prelab Exercise: Give the detailed mechanism for the acid-catalyzed hydrolysis of methyl benzoate. Introduction: The ester group is an important functional group that can be synthesized in a number of different ways. The low-molecular-weight esters have very pleasant odors and indeed are the major components of the flavor and odor aspects of a number of fruits. Although the natural flavor may contain nearly a hundred different compounds, single esters approximate the natural odors and are often used in the food industry for artificial flavors and fragrances.

Esters can be prepared by the reaction of a carboxylic acid with an alcohol in the presence of a catalyst such as concentrated sulfuric acid, hydrogen chloride, p-toluenesulfonic acid, or the acid form of an ion exchange resin: O C H3C + CH OH 3 OH H+ H3C O O CH3 + H O 2

This Fischer esterification reaction reaches equilibrium after a few hours of refluxing. The position of the equilibrium can be shifted by adding more of the acid or of the alcohol, depending on cost or availability. The mechanism of the reaction involves initial protonation of the carboxyl group, attack by the nucleophilic hydroxyl, a

proton transfer, and loss of water followed by loss of the catalyzing proton to give the ester. Because each of these steps is completely reversible, this process is also, in reverse, the mechanism for the hydrolysis of an ester:

Other methods are available for the synthesis of esters, most of them more expensive but readily carried out on a small scale. For example alcohols react with acid anhydrides to form esters: O CH3CH2OH Ethanol + O H3C O O CH2CH3 + CH3COOH Acetic acid

C C H3C CH3 O Acetic anhydride

Ethyl acetate

Acid chlorides form esters by reaction with alcohols.
O CH3CH2CH2OH 1-Propanol + H3C Cl Acetyl chloride C H3C O C O

CH2CH2CH3 + HCl

n-Propyl acetate

In the latter reaction, an organic base such as pyridine is usually added to react with the hydrogen chloride. A number of other methods can be used to synthesize the ester group. Among these are the addition of 2methylpropene to an acid to form t-butyl esters, the addition of ketene to make acetates, and the reaction of a silver salt with an alkyl halide. O CH3CH2C OH + CH2 2-Methylpropene (isobutylene) CH3 C CH3 H+ O CH3 CH3 t-Butyl propionate O CH2 C O + HOCH2 Benzyl alcohol CH3 C OCH2 CH3CH2C O C CH3

Propionic Acid

Ketene

Benzyl Acetate

O CH3C O- Ag+ Silver acetate
+

CH3 BrCH2CH2CH CH3 1-Bromo-3-methylbutane

O CH3 CH3C O CH2CH2CH CH3 Isoamyl acetate

As noted above, Fischer esterification is an equilibrium process. Consider the reaction of acetic acid with 1butanol to give n-butyl acetate: O H3C C OH Acetic acid + HOCH2CH2CH2CH3 n-Butanol

H+

O CH2CH2CH2CH3 C + H2O O H3C n-Butylacetate

The equilibrium expression for this reaction is shown below.

O H3C C O O H3C C OH CH2 CH2CH2 CH3 [H2O]

Keq=

[HOCH2CH2CH2CH3]

For primary alcohols reacting with unhindered carboxylic acids, Keq ~4. If equal quantities of 1-butanol and acetic acid are allowed to react, at equilibrium the theoretical yield of ester is only 67%. To upset the equilibrium we can, by Le Chatelier's principle, increase the concentration of either the alcohol or acid, as noted above. If either one is doubled, the theoretical yield increases to 85%. When one is tripled, it goes to 90%. But note that in the example cited the boiling point of the relatively nonpolar ester is only about 8 C higher than the boiling points of the polar acetic acid and 1-butanol, so a difficult separation problem exists if either starting material is increased in concentration and the product is isolated by distillation. °

Another way to upset the equilibrium is to remove water. This can be done by...
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