Classification Tests for Carboxylic Acid and Derivatives

Eunice Mae D, Del Valle, Mary Coleen A. David, Sean Romeo B, Desagon, Maria Cauline M.
Fang, Jenicca Pamela Y. Go, Jan Chretien M. Guillo
Group 3, 2F-PH, Faculty of Pharmacy, Univeristy of Santo Thomas

ABSTRACT
Carboxylic acid and their derivatives are a type of carbonyl group that
contains a carbon double-bonded to oxygen. These organic compounds
contain an acyl group core structure attached to an electronegative atom or
substituent that acts as a leaving group in necleophilic acyl substitution.
Several classification tests are used to distinguish carboxylic acid derivatives
and determine its reactivities. The tests done were the hydrolysis, alcoholysis
(Schotten-Baumann Reaction), aminolysis, and hydroxamic acid test. The
reagents used are acetyl chloride representing acyl halides, acetic anhydride
representing acid anhydrides, ethyl acetate representing esters and
acetamide and benzamide representing amides. Those that give positive
results to the test, imply that carboxylic acid is present. Ethyl acetate and
acetamide was observed to have deep burgundy color.
INTRODUCTION
Carboxylic acid is a compound containing a carboxyl group that has a
carbonyl group and a hydroxyl group on the same carbon atom. Carboxylic
acids tend to be high-boiling and viscous because the molecules associate
together through strong hydrogen bonds. Carboxylic acids are highly oxidize,
thus they are often made oxidation of other compounds. Primary alcohols
and aldehydes oxidize to acids, while alkenes and alkynes undergo oxidative
cleavage to acids.
The functional groups that undergo nucleophilic acyl substitutions are called
carboxylic acid derivatives: these include carboxylic acids themselves,
carboxylates, amides, esters, thioesters, and acyl phosphates. Two more
examples of carboxylic acid derivatives which are less biologically relevant
but important in laboratory synthesis are carboxylic acid anhydrides and acid
chlorides. The carboxylic acid derivatives can be distinguished from
aldehydes and ketones by the presence of a group containing an
electronegative heteroatom, usually oxygen, nitrogen, or sulfur bonded
directly to the carbonyl carbon. A carboxylic acid derivative as having two
sides. One side is the carbonyl group and the attached alkyl group: this is
called an acyl group. The difference in structure leads to a major change in
reactivity.
More reactive acid derivatives easily react gives less reactive derivatives,
Their reactivity decreases in the following order: acyl halides, acid
anhydrides, esters, amides, and carboxylate ions. Most of interconversions
take place by nucleophilic acyl substitution wherein a nucleophile adds to the

carbonyl group to give a tetrahedral intermediate, and then a leaving group

leaves, regenerating the carbonyl group. Any factors that make the carbonyl
group more easily attacked by the nucleophile favor reaction. Some of these
factors include: steric and electronic factors which affect the reactivity of the
acid derivative towards nucleophilic acyl substitution reactions; steric factors
wherein unhindered, accessible carbonyl groups react with nucleophiles
more readily than do steric hindered groups; and electronic factors wherein
strongly polarized acid derivatives are attacked more readily than less polar
ones.
Carboxylic acids and their derivatives are usually seen in industrial processes
and most biological pathways. Esters can be seen as fats and within the cell
membrane. Esters are also present in pleasant smelling liquids that are
responsible with the fragrant odor of fruits and flowers. Amides are also
present in animal protein and also in industrial products such as nylon. Acid
chlorides and acid anhydrides are used in the synthesis of carboxylic
derivatives. These are not usually found in nature because of its high
reactivity property.

METHODS

1. Hydrolysis of Acid Derivatives

a. Acyl halides and Acid anhydrides
1 ml of water was placed in a test tube. 10 drops of the sample, namely
acetyl chloride and acetic anhydride, was added in a drop wise manner. A
warming effect was noted. The first resulting mixture was divided into two
portions. To the first portion, 1 ml of 2% AgNO3 was added. Precipitation was
observed. To the second portion, 1 ml of saturated NaHCO3 was added. An
evolution of gas was observed.
b. Esters
2ml of 25%NaOH solution was added to 1 ml of ethyl acetate. The
mouth of the test tube was covered and the test tube was heated
in boiling water bath for 5 minutes. The mixture was then
neutralized with 10% HCl solution. With a wafting motion, the odor
of the solution was noted.
c. Amides
1ml of benzamide was treated with 5 mml 10% NaOH solution. The
solution was then heated to boiling. While heating, the test for the
reaction gas evolution was done by holding a piece of moist red
litmus paper over the heated test tube.

2. Alcoholysis: Schotten-Bauman Reaction

a. Acetic Acid
A mixture of 10 drops of acetic acid, 1ml ethanol and 5 drops of
conc. H2SO4 was warmed over a water bath for 2 minutes. The
odor of the ester formed was noted.
b. Acyl halides and Acid Anhydrides
In another test tube, a mixture of 0.5 ml ethanol, 1ml water, and
0.2ml of acyl halide or acid anhydride was prepared. 2ml of 20%
NaOH solution was then added. The test tube was covered with
paraffi n wax and was shook for several minutes. An odor of the
formed ester and a formation of two layers were noted.
3. Aminolysis: Anilide Formation
A few drops of acetyl chloride or acetic anhydride was added to
0.5ml of aniline. The mixture was transferred to a new test tube
containing 5ml of water. The formation of a precipitate was noted.
4. Hydroxamic Acid Test
The preliminary test was done by mixing 2 drops of the sample, 1
ml of 95% ethanol and 1M HCl, A drop of 5% FeCl3 solution was
added to the mixture and the color produced was noted. If the
color other than yellow was obtained, the test cannot be used.
Otherwise, another test was conducted as follows:
2 drops of the sample was added to 2ml of alcoholic NH2OH*HCl
and 1ml of KOH. The solution was heated in a boiling water bath
for 2 minutes. The mixture was cooled. 1ml of 5% FeCl3 was then
added. A formation of deep burgundy color was observed.

RESULTS AND DISCUSSION