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ESTERIFICATION: PREPARATION OF BENZYL ACETATE

MICROSCALE EXPERIMENT IV

O
R C O R'

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 odours and indeed are major

components of the flavour and odour aspects of a number of fruits. Although the natural flavour

may contain nearly a hundred different compounds, single esters approximate the natural odours

and are often used in the food industry for artificial flavours and fragrances (see Table on p. 40).

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 by using the acid form of an ion-exchange resin, for example:

O O
HCl
CH3 C O H CH3OH CH3 C O CH3 H 2O
acetic acid methanol methyl acetate

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 group of the alcohol, a proton transfer,

and loss of water, followed by deprotonation 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.
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TABLE. Fragrances and Boiling Points of Esters

Boiling
Ester Formula Fragrance
Point (C)
O CH3

Isobutyl formate HCOCH2CHCH3 98 Raspberry

O
n-Propyl acetate
CH3COCH2CH2CH3 102 Pear

O
Methyl butanoate
CH3CH2CH2COCH3
102 Apple
O
Ethyl butanoate CH3CH2CH2COCH2CH3 121 Pineapple

O CH3
Isobutyl
propanoate CH3CH2COCH2CHCH3 137 Rum

O CH3

Isoamyl acetate CH3COCH2CH2CHCH3 142 Banana

Benzyl acetate CH3COCH2 206 Peach

O
Octyl acetate CH3COCH2(CH2)6 CH3 210 Orange

O
Methyl salicylate COCH3 222 Wintergreen

OH
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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 anhydrides and with acid

chlorides:

O O O O
CH3CH2OH + CH3C O CCH3 CH3COCH2CH3 + CH3COH
Ethanol Acetic anhydride Ethyl acetate Acetic acid

O O
CH3CH2CH2OH + CH3CCl CH3COCH2CH2CH3 + HCl
1-Propanol Acetyl chloride n-Propyl acetate

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 2-methylpropene to an acid to form t-butyl esters and the reaction of a silver salt

with an alkyl halide:

CH3 O O CH3
H+
CH2 CCH3 + CH3CH2COH CH3CH2COCCH3
CH3
2-Methylpropene Propanoic acid t-Butyl propanoate
(isobutylene) (propionic acid)

O CH3 O CH3
CH3CO-Ag+ + BrCh2CH2CHCH3 CH3COCH2CH2CHCH3
Silver acetate 1-Bromo-3-methylbutane Isoamyl acetate

As noted above, Fischer esterification is an equilibrium process. Consider the reaction of

acetic acid with 1-butanol to give n-butyl acetate:

O O
CH3COH + HOCH2CH2CH2CH3 H+
CH3COCH2CH2CH2CH3 + H2O
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The equilibrium constant is given by

K eq =
[n BuOAc][H 2 O]
[n BuOH][H 2 OAc]
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 Chteliers 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 8C 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 adding to

the reaction mixture molecular sieves, an artificial zeolite, which preferentially adsorb water.

Most other drying agents, such as anhydrous sodium sulfate or calcium chloride, will not remove

water at the temperatures used to make esters.

Reference:

Organic Chemistry (5th edn., 2000) by J. McMurry; Sections 21.3, 21.6.

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Experimental Procedure Preparation of Benzyl Acetate from Acetic Anhydride and Benzyl

Alcohol

O O O O
CH2OH2 + CH3C O CCH3 CH2OCCH3 + CH3COH

To a round bottomed flask add 108 mg of benzyl alcohol and 102 mg of acetic anhydride and a

boiling chip. Reflux the mixture for at least 1 hour, cool the mixture to room temperature, and

chromatograph the liquid as follows: Assemble the column as

shown in the Figure, being sure it is clamped (with one clamp) in

a vertical position. Close the valve and fill of the column with

dichloromethane DICHLOROMETHANE IS VERY

VOLATILE to the bottom of the funnel. Prepare a slurry of

10 mL silica gel in 4 mL of dichloromethane in a small beaker.

Stir the slurry gently to get rid of air bubbles and gently swirl,

pour and scrape the slurry into the funnel. After some of the

silica gel has been added to the column, allow the solvent to

drain slowly into an Erlenmeyer flask. Use this dichloromethane

to rinse the beaker containing the silica gel. As the silica gel is

being added, VERY GENTLY tap the column with a pencil so

the adsorbent will pack tightly into the column. Continue to tap

the column while cycling the dichloromethane through the column once more and then add a

sample of anhydrous potassium carbonate to the top of the silica gel. The potassium carbonate

will remove water from the esterification mixture as well as react with any carboxylic acid

present. Run the solvent down to the surface of the potassium carbonate.

Using a Pasteur pipet, add the sample to the column and let it run into the adsorbent,

stopping when the solution reaches the top of the potassium carbonate. The flask is rinsed twice
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with 0.5 mL portions of dichloromethane that are run into the column, with the eluent being

collected in a tared sample bottle. The elution is completed with 4 mL more dichloromethane.

Evaporate the dichloromethane on the steam bath in the hood. Since the dichloromethane

boils at 40C and the product at 206C, separation of the two is easily accomplished. Determine

the weight of the product and calculate the yield. The ester should be a perfectly clear,
1
homogeneous liquid. An IR spectrum and a H NMR spectrum of benzyl acetate are supplied.

Analyze it for the presence of unreacted alcohol and acetic anhydride. (These spectra can be

found on page 45 - 47.)

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