Esters

1. Hydroxamic acid Test (Positive Test: A positive test is formation of a blue-red

color)
PROCEDURE:
Place 50 mg or 2 drops of the unknown or reference compound along with 1 mL
of 0.5 M hydroxylamine hydrochloride in methanol in a test tube. Add 2.5 M
sodium hydroxide solution drop-wise until the mixture is alkaline (use pH paper).
Then add 3 drops more of the sodium hydroxide solution. Heat the reaction
mixture just to boiling, cool the tube, and add 1.5 M hydrochloric acid dropwise
with shaking until the pH of the mixture is 3. Add 2 or 3 mL more of methanol if a
cloudy mixture results. Then add 1 drop of 0.7 M ferric chloride solution. A
positive test is formation of a blue-red color. Try the test on one or two esters and
on phenol as reference compounds.
CLEANUP:
Place the entire reaction mixture in the container for inorganic waste. Esters react
with hydroxylamine in basic solution to form hydrox-amic acids, which in turn
react with ferric chloride in acidic
solution to form bluish red ferric hydroxamates:

Ferric chloride reacts directly with phenols to give products of much the
same color, and some phenols may interfere with this test. However, the acidic
solution used here usually converts a ferric-phenolate complex into a free phenol,
which is not deeply colored.

2. Esther Hydrolysis
PROCEDURE:
Place 1 g of the unknown or reference ester and 10 mL of 2.5 M sodium
hydroxide in a 50-mL round-bottomed flask equipped with a reflux condenser.
Reflux the mixture for 1 h, then extract the cooled product with two 20-mL
portions of diethyl ether. After drying the ether solution, distill it to obtain the
alcohol. Identify the alcohol.
Make the aqueous sodium hydroxide solution distinctly acidic with 1.5 M
HCl and cool well. If a precipitate forms, collect the solid by vacuum filtration. If
no precipitate forms, extract the solution with two 20-mL portions of diethyl ether.
Dry the ether solution and distill it. Identify the carboxylic acid residue.

CLEANUP:
Pour the recovered ether solutions into the container for flammable organic
waste. Neutralize the aqueous filtrate with sodium carbonate before placing it in
the container for aqueous inorganic waste or washing it down the sink.
Basic hydrolysis converts an ester into the carboxylate salt of the parent acid and
the alcohol from which the ester was formed. Acidification of the carboxylate salt
solution with HCl leads to the recovery of the parent acid.

Often you will find that either the carboxylic acid or the alcohol formed
from the hydrolysis of an ester is extremely soluble in water and does not appear
in the ether extract. This situation occurs with ethyl benzoate and 1-phenylethyl
acetate, for example. Whereas the benzoic acid is easy to isolate, most of the
ethanol remains in the water solution. Similarly, the 1-phenylethanol can be
readily extracted with ether, but this is not so for the acetic acid. In these cases,
you may have to rely on a definite identification of the water-insoluble component
and combine this evidence with the physical and spectral data
for the unknown ester in order to reach a final answer.