Classification Tests for Carboxylic Acid and Derivatives

K. Manlangit, J. Manuel, S.F. Manugas, J. Ongsitco, M.A. Pasciolco*

Faculty of Pharmacy, University of Santo Tomas, 2010

Abstract
Carboxylic acid and derivatives are a type of carbonyl group that contains a carbon double-
bonded to oxygen. These compounds have a common structural feature which is they contain an acyl
group bonded to an electronegative atom or substituent that can act as a leaving group. The experiment’s
objectives are to determine the reactivities of carboxylic acid derivatives and to distinguish carboxylic acid
derivatives using several classification tests. The reactions involved in each test are explained through
chemical equations and mechanisms. To accomplish the objectives of the experiment, the tests done
were the hydrolysis, alcoholysis, aminolysis and hydroxamic acid test. Those that give positive results to
the test inferred that carboxylic acid is present. Ethyl acetate and acetamide was observed to possess a
deep burgundy discoloration. It is important to use a clean and dry test tube because a little water can
react to the samples which may give the experiment unnecessary or unwanted results.

Introduction

Carboxylic acids and their

derivatives are the most abundant of all
organic compounds in living organisms
and in laboratory. The most common
derivatives of carboxylic acids are acyl
halides, acid anhydrides, esters, and
amides. They contain acyl group
attached to a nucleophilic molecule that
replaced the -OH group of a carboxylic
acid. Carboxylic acids and their
derivatives are involved in many
industrial processes and most biological
pathways (1). Acyl halides are used as a
starting material for synthesis due to its
reactivity. Amides, like acids and esters,
are abundant in living organisms-
proteins, nucleic acids, and many
pharmaceuticals have amide functional
group (2).
All carboxylic acid derivatives
yield the parent carboxylic acid upon
reaction with water. Furthermore, one
derivative can be converted into
another, provided the former is more
reactive than the latter (3). Carboxylic
acid derivatives react with the same
mechanism the nucleophile attacks the
carbonyl carbon, forming an unstable
tetrahedral intermediate, which modifies
a carboxylic acid derivative by
eliminating the weakest base. The types
of nucleophilic acyl substitution that a
carboxylic acid derivative undergoes are
hydrolysis, aminolysis and alcoholysis
(4).
The experiment aimed to
differentiate the reactivities of carboxylic
acid derivatives and to distinguish it
using classification tests. It also aimed
to explain through chemical equation
and mechanisms the reactions involved
in each tests.
 Methodology
D. Hydroxamic Acid Test
A. Hydrolysis of Acid Derivatives Preliminary test: Two drops of the
sample was mixed with 1mL of 95%
Acid Halides and Acid Anhydrides ethanol and 1 M HCl. The color
In a test tube, 1 mL of water was produced when 1 drop of 5%FeCl 3
placed and then 10 drops of the sample solution is added was noted. If color
was cautiously added dropwise. The other than yellow is obtained the test
resulting mixture was divided into two cannot be use. Otherwise, it is
portions. 1 mL of 2% AgNO was added conducted as follows:
to the first test tube while 1mL of
saturated NaHCO3 was added to the 2nd In another test tube, 2 drops of the
portion. sample was added to 2 mL of alcoholic
NH2OH•Cl and 1 mL KOH. The mixture
Esters was heated in a boiling water bath for 2
In 1 mL of ethyl acetate, 2 mL of minutes. It was the cooled and
25% NaOH was added. The mouth of combined with 1 mL of 5%FeCl3.
the test tube was covered with marble
and heated in a boiling water bath for Results
5mins. The mixture was then neutralized Results obtained from the Hydrolysis of
with 10%HCl. Acid Derivatives were tabulated as
shown in table 1.
Amides
In a test tube, 1 mL of Hydrolysis of Acid Observations
benzanamide was treated with 5 mL of Derivatives
10% NaOH and heated to boiling. The Acyl Halides and acid
reaction of the gas evolved was tested anhydrides
by holding a piece of moist red litmus Acetyl chloride White precipitate with
paper over test tube during heating. evolution of gas
Acetic anhydride No precipitate with
B. Alcoholysis: Schotten-Baumann evolution of gas
Reaction Esters
A mixture of 10 drops of acetic acid, Ethyl acetate Plastic balloon-like
1 mL ethanol and 5 drops of odor
concentrated H2SO4 was warmed over a Amides
water bath for 2 mins. Then 0.5 mL of Benzamide Red to Blue litmus
paper (Base)
ethanol, 1 mL of water and 0.2 mL of Table 1. Results observed from the hydrolysis of
acid halide or acid anhydride sample acid derivatives.
was placed in another test tube. 2mL of
20%NaOH was added. The test tube Results obtained from Alcoholysis were
was stopped with a cork or parafilm and tabulated as shown in table 2.
the mixture was shook for several times.
Alcoholysis Observations
C. Aminolysis: Anilide Formation
Few drops of acetyl chloride or Acetic acid Plastic balloon-like
acetic anhydride sample was added to odor
Acetyl chloride Fruity odor
0.5mL aniline. The mixture was
Table 2. Results observed from alcoholysis of
transferred to a new test tube with 5ml acetic acid and acetyl chloride.
of water.
 Benzamide yields ethanoic acid
plus amine upon heating in 5 mL of
10% NaOH solution. The resulting
Results obtained from Aminolysis were
vapor from the reaction upon testing
tabulated as shown in table 3.
with moist litmus paper was basic due
to the basic nature of amine (NH3) (6).
Aminolysis Observations
Acetyl chloride Yellow oily layer RCONH2 + NaOH ---> RCOO-Na+ + NH3.
Acetic anhydride Whitish-yellow
precipitate In alcoholysis, acetyl chloride and
Table 3. Results observed from the aminolysis acetic anhydride upon reaction with
of acetyl chloride and acetic anhydride. ethanol and H2SO4 formed an ester
which gave the agreeable odor of the
mixture.
Results obtained from Hydroxamic Acid
Test as shown in table 4. In aminolysis, the formation of the
oily layer was the result of the
difference in density and solubility of
Hydroxamic Acid Observations the compounds. White precipitate was
Test also formed due to the presence of
Preliminary Test Ethyl acetate and anilide in the mixture which was yield
acetamide turned into upon addition of water.
a yellow solution
Ethyl acetate Deep burgundy In the hydroxamic acid test, a
discoloration yellow coloration of the resulting
Acetamide Deep burgundy mixture during the preliminary test
discoloration
proved the enolic character of the
Table 4. Results observed from the Hydroxamic
acid test of ethyl acetate and acetamide. mixture. Ethyl acetate and acetamide
were converted to hydroxamic acid
upon heating with NH2OH•Cl. The deep
Discussion burgundy discoloration of ethyl acetate
and acetamide was obtained from the
In the hydrolysis of acyl halides reaction of hydroxamic acid with FeCl3.
and acid anhydrides, a warming effect
was observed due to exothermal It can be concluded from the
reaction and formation of the acetic experiment that carboxylic acid and
acid, the parent carboxylic acid. The derivatives can be classified by different
gas that evolved during effervescence classification tests. The types of
of the addition of 2% AgNO3 and nucleophilic acyl substitution that a
saturated NaHCO3 in acetyl chloride carboxylic acid derivative undergo are
was due to the evolution of CO 2 gas hydrolysis, aminolysis and alcoholysis
(5). and using the gathered positive result,
the presence of the particular carboxylic
An aqueous base, 25 % NaOH acid derivatives can be determined.
was used to hydrolyze ethyl acetate I can say that from the points discussed,
yielding acetic acid with alcohol which the experiment successfully met its
gives a plastic balloon-like odor to the objectives.
sample.
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