CLASSIFICATION TESTS FOR CARBOXYLIC ACID AND DERIVATIVES

Cavida, C.M., Chosantos, D.B., Chua, K.B.W., Co, E.K.T. and *Crisol, A.M.L. Group 2, 2C ± MT, Faculty of Pharmacy, UST

Abstract There are different tests for the classification of carboxylic acids and its derivatives. These tests, namely, hydrolysis, alcoholysis, aminolysis and hydroxamic acid test were performed on the individual compounds to yield positive or negative results that will determine the presence or absence of a particular carboxylic acid and its derivatives. Acyl halides, acid anhydrides, esters and amines are called carboxylic derivatives and the sample compounds used for each functional group were acetyl chloride, acetic anhydride, ethyl acetate, and acetanamide and benzanamide respectively.

I.

Introduction 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 the 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 sterically hindered groups; and electronic factors wherein strongly polarized acid derivatives are attacked more readily than less polar ones. The types of nucleophilic acyl substitution that a carboxyl acid derivative undergoes are hydrolysis, aminolysis and alcoholysis. Hydrolysis involves a reaction with water to yield a carboxylic acid. Aminolysis involves a reaction with alcohol to yield an ester. Aminolysis involves a reaction with ammonia or amine to yield an amide.

A carboxylic acid is a compound containing a carboxyl group, R-COOH, 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 oxidized, thus they are often made by oxidation of other compounds. Primary alcohols and aldehydes oxidize to acids, while alkenes and alkynes undergo oxidative cleavage to acids. Carboxylic acid derivatives are compounds with functional groups that can be converted to carboxylic acids by a simple acidic or basic hydrolysis. They include esters, amines, nitriles, acyl halides, and acid anhydrides. These groups of compounds also contain a carbonyl group, but now there is an electronegative atom (oxygen, nitrogen, or a halogen) attached to the carbonyl carbon. In general, more reactive acid derivatives easily react to give less reactive derivatives. Their reactivity decreases in the following order: acyl halides, acid anhydrides, esters, amides, and carboxylate ions. Most of these

The tetrahedral intermediate undergoes elimination of Cl. This reaction is a typical nucleophilic acyl substitution process. Hydroxamic Acid Test A preliminary test was done first by mixing 2 drops of the sample. The mixture was then neutralized with 10% HCl solution. Aminolysis: Anilide Formation 0. Results and Discussion Hydrolysis of Acid Derivatives In hydrolysis. The resulting mixture was divided into two portions. For amides. 1 mL of ethanol and 5 drops of concentrated H2S04 was warmed over a water bath for 2 minutes. The odor of the ester that was formed was noted. On the 1st portion. 2 mL of 25% NaOH solution was added to 1 mL of ethyl acetate. The resulting mixture was then heated in a boiling water bath for 2 minutes. the odor was observed. A cork or a parafilm was placed on the test tube which was then shaken for several minutes. acetyl chloride and acetic anhydride were cautiously added to two separate test tubes. 2 mL of 20% NaOH was added to a mixture of 0. The odor of the ester that was formed and the formation of two layers were noted. 1 mL of saturated NaHCO3 was added. namely. 5 mL of 10% NaOH solution was added to 1 mL of benzanamide. 4. For esters. Formation of precipitate was observed. and 0.2 mL of acyl halide or acid anhydride sample. initiated by the attack of water on the acyl halide carbonyl group. The indication of a positive result is the formation of a deep burgundy color. 3. acyl halides react with water to yield carboxylic acids. 2. A color produced other than yellow means that the test cannot be used. 1. A formation of precipitate was noted. With a wafting motion. 10 drops of the samples. The mixture was then heated to boil. The resulting mixture was then transferred to new test tube containing 5 mL of water. Otherwise. acetyl chloride and acetic anhydride.5 mL aniline was added to the sample compounds. 1 mL of water. On the 2nd portion. The reaction of the gas evolved was tested by placing a piece of moist red litmus paper over the test tube. Methodology 1. Evolution of gas was then noted. In another test tube. III. each of which contains 1 mL of water. The mouth of the test tube was covered with a marble and then heated in a boiling water bath for 5 minutes. the test proper was done by adding 2 drops of the sample to 2 mL of alcoholic NH2OH*HCl and 1 mL of 1 M KOH.5 mL of ethanol. Afterwards. 1 mL of 95% ethanol and 1 M HCl. Alcoholysis: Schotten-Baumann Reaction A mixture of 10 drops of acetic acid. A warming effect was noted on each test tube.and loss of . the mixture was cooled and was added with 1 mL of 5% FeCl3. 1 mL of 2% AgNO3 was added.II. The color produced when 1 drop of 5% FeCl3 solution is added to the mixture was then noted. Hydrolysis of Acid Derivatives For acyl halides and acid anhydrides.

Results observed on Hydrolysis of Carboxylic Acid Derivatives A warming effect was observed in the hydrolysis of both acetyl chloride and acetic anhydride. ALCOHOLYSIS Acetyl chloride Acetic anyhydride OBSERVATIONS Vinegar-like odor Plastic balloon-like odor w/ H20 Warming effect Warming effect Table 2. In the alcoholysis of acetic anhydride. During the test. A deep burgundy . formation of bubbles indicated the presence of carboxylic acid. Acid anhydride also reacts but it takes a longer time. Alcoholysis: Reaction Schotten ± Baumann Acyl halides react rapidly with ammonia or amines to yield an anilide upon addition of water. However. 2. in which case acetyl chloride was faster than acetic anyhydride. Upon adding 2% AgNO3. 3. a preliminary test was done to eliminate those phenols and enols that give colors with ferric chloride in acidic solution that would therefore give false positive result in the ferric hydroxamate test. This confirms the presence of an ester. Both acetyl chloride and acetic anhydride had the same result upon addition of saturated NaHCO3: there were no precipitates formed. a plastic balloon-like odor and a formation of two layers were observed which confirmed the presence of an ester.H+ to give the product carboxylic acid and HCl. Results observed on Alcoholysis of Acetic chloride and Acetic anhydride ³thinner-like´ odor Basic (red->blue litmus paper) A vinegar-like odor was observed during alcoholysis of acetyl chloride. HYDROLYSIS Acid Halides and Anhydrides Acetyl chloride Acetic anhydride Ester Ethyl Acetate Amide Benzanamide OBSERVATIONS w/ 2% AgNO3 White ppt No ppt w/ saturate d NaHCO3 No ppt No ppt mechanism except for the rate of their reaction. both ethyl acetate and acetanamide yielded a yellow color indicating that the test proper should proceed. Hydroxamic Acid Test An ester was formed during alcoholysis of acetyl chloride and acetic anhydride. Upon heating with hydroxylamine. ethyl acetate and acetanamide were converted to hydroxamic acid. Formation of white precipitate on both sample compounds was due to the presence of anilide in the mixture. no precipitate was formed. Both samples have the similar Before proceeding to the test proper. A thinner-like odor during heating of ethyl acetate confirmed the presence of an ester. a white precipitate was formed on acetyl chloride. A red litmus paper turned blue accompanied by an amine-like odor indicated the presence of an amide during the hydrolysis of benzanamide which yielded ethanoic acid and amine. AMINOLYSIS Acetyl chloride Acetic anyhydride OBSERVATIONS White ppt White ppt Table 3. Results observed on Aminolysis of Acetic chloride and Acetic anhydride 4. Aminolysis: Anilide Formation Table 1. whereas on acetic anhydride.

. Laboratory Manual in Organic Chemistry. References BOOKS: Bayquen. from http://chemistry2. (2010). from http://www2. (2005). et al (2009). Washington: Chemical Publishing Co. 2010.csudh. Acid Test OBSERVATIONS Both with yellow discoloration Deep burgundy discoloration Deep burgundy discoloration Results observed on Hydroxamic IV.htm Retrieved September 25. 2010.. Pasay City: Cengage Learning Asia Pte Ltd. Cruz.chemistry. A. WEBSITES: Retrieved September 25.V. J. L.T.html . HYROXAMIC ACID TEST Preliminary Test Ethyl acetate Acetanamide Table 3. Foundations of Organic Chemistry. Inc. 5th Edition. Organic Chemistry. C. McMurry.msu..G.discoloration of the compound confirmed its positivity.edu/faculty/r eusch/VirtTxtJml/crbacid1. Quezon City: C&E Publishing Inc Wade.edu/rpendarvis/c arboxder.

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