Zeisel Test

Functional Group(s): esters and ethers

Known(s): Ester: methyl benzoate
Ether: anisole

Procedure
Set up three medium test tubes in a test tube rack and label them #1-3. Add ~100mg of a solid unknown or ~100µl of a liquid
unknown to tube #1. Add ~100µl of methyl benzoate to tube #2 and ~100µl of anisole to tube #3. Add 1 ml of acetic acid, 1 ml of
57% hydriodic acid (HI) and 1 small piece of unglazed porcelain to each tube. Using a ruler, measure 4cm down from the top of each
test tube and mark 4 cm with a permanent marker.

Using tweezers, obtain three pieces of treated, rolled gauze, one for each tube. (Gauze is rolled to fit the appropriate size test tubes.)
Insert the gauze into each tube so that the top of the gauze is just below the 4 cm mark on the tube. Obtain three cotton balls. Gently
tamp one cotton ball into each tube just above the gauze. The cotton disk should be 2-3 cm thick. Obtain three strips of filter paper
(~2cm X 10 cm) and fold each strip longitudinally. Using gloves and tweezers, dip the filter paper in a solution of mercuric nitrate,
allowing excess solution to drip back into the bottle. Place one filter paper strip on top of the cotton plug. Clamp the tubes to a ring
stand and immerse them in a silicon oil bath set on top of a hot pate stirrer. Suspend a thermometer from a ring attach to the ring stand
into the silicon bath. Heat the tubes for 6-8 minutes in the silicon oil bath to 120-130oC. As the reaction mixture is heated, the gauze
and cotton plug usually turn gray. Observe the filter paper for a color change to orange or red. Compare the results obtained for the
unknown with those obtained for the known compounds.

Results
The formation of an orange or red color on the filter paper is indicative that the unknown contains an ester or an ether. Some alcohols
may give positive results.

Theory
Treatment of an ether or an ester with hydriodic acid causes and acid catalyzed cleavage of the ester or ether functional group through
an SN1 mechanism. An alkyl iodide and an alcohol is generated from an ether and an alkyl iodide and a carboxylic acid is generated
from an ester. As the reaction mixture is heated, the volatile alkyl halide that is generated in the reaction rises and encounters the
mercuric nitrate on the filter paper strip. The alkyl iodide reacts with the mercuric nitrate to generate mercuric iodide, which is orange
or red.

This test works well for methoxy-, ethoxy- and propoxy- ethers. Larger alkyl ethers tend to give negative results because the alkyl
iodide product is not volatile enough to reach the filter paper and react with the mercuric nitrate.
Zeisel Test
Functional Group(s): esters and ethers
Known(s): Ester: methyl benzoate
Ether: anisole

H-I H CH3OH

O +
O H3C
H3C

Ether
I

HgNO2
HgI CH3I
Orange

H-I H HO

O
O H3C
H3C CH3
O
O
I
Ester

HgNO2
HgI
CH3I
Orange