Classification Tests for Carboxylic Acid and Derivatives

Regina Loren L. Soriano, Jeremae K. Tan, Hazel Joy M. Tequillo, Michelle S. Tolentino and Nina Maria Inez A. Torno Group 8 2F Pharmacy Organic Chemistry Laboratory

ABSTRACT
Carboxylic acids are organic compounds which have at least one carboxyl group with a general formula of R-COOH. Carboxylic acids have derivatives which are defined as organic compounds containing a carbonyl group with an electronegative atom (oxygen, nitrogen or halogen) attached to the carbonyl carbon. Among these carboxylic acid derivatives, acyl halides are the most reactive and amides the least. Reactions of carboxylic acids yield esters, salts and acyl chlorides. The experiment used reagents to test the presence of carboxylic acid and used reagents like acyl chloride representing acyl halides; acetic anhydride representing acid anhydrides; ethyl acetate representing esters and acetanamide and benzamide representing amides. With the test, yielding a positive result confirms the presence of carboxylic acid group. acids and it derivatives. The different classification INTRODUCTION tests for such are also observed. Carboxylic acid derivatives are a group of organic compounds containing a carbonyl group with electron negative atoms attached to the carbonyl atom. With the different electron negative atoms attached, this difference in structure leads to a major change in reactivity. Nucleophilic substitution is the reaction involve with these groups of compound, wherein the substitution of the electronegative atom by a nucleophile occurs. Although there are abundant kinds of carboxylic acid derivatives, the experiment only focuses on the common ones: acid halides, acid anhydrides, esters and amides. Esters are found in fats and cell membrane, amides are found in nylon and proteins, acyl chloride (acyl halide) are found in the synthesis of carboxylic acids and same with acid anhydride. A property of carboxylic acids is acidity meaning most are made to react with bases to yield water soluble metal carboxylates. Nucleophilic substitution reaction of carboxylic acids and its derivatives yields the formation of alcohol. Initially an intermediate product is formed then it expels one of its substituents which is originally bonded to the carbonyl carbon forming a new carbonyl compound. The reaction is called nucleophilic acyl substitution reaction. Hydrolysis is a reaction with water to yield a carboxylic acid, and this is the procedure for acyl halides, acid anhydrides, esters and amides. Also for acetyl chloride is alcoholysis: Schotten-Bauman Reaction. It is the reaction with an alcohol to yield an ester. The alcohol used here was ethanol. For acetyl chloride and acetic anhydride, the reaction used was aminolysis: anilide formation. Aminolysis is the reaction with ammonia or amine to yield an amide. In this case, aniline was the ammonia and anilide, an amide, was produced. Hydroxamic acis test was used for ethyl acetate and acetamide. Through this experiment, students are able to visualize, through the different reactions, the nuecleophilic acyl substitution reaction for carboxylic

EXPERIMENTAL A. Compound tested

Acyl chloride Acid anhydrides Esters Amides

B. Procedure
A. Hydrolysis of Acid Derivatives Acyl halides and Acid anhydrides 1 ml of water was placed in a test tube and 10 drops of the sample, in this case acetyl chloride and acetic anhydride, was added drop wise. A warming effect was then noted. The mixture was then divided into two portions. To the 1st, 1 ml of 2% AgNO3 was added. Precipitation was observed. To the second mixture, 1 ml of saturated NaHCO3 was added. An evolution of gas was observed. 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 a boiling water bath for about 5 minutes. The mixture was then neutralized with 10% HCL solution. With a wafting motion, the odor of the solution was noted. Amides: 1ml of benzamide was treated with 5ml of 10% NaOH solution. The solution was then heated to boiling. While heating, the test for the reaction of gas evolution was done by holding a piece of moist red litmus paper over the heated test tube. B. Alcoholysis: Schotten-Baumann Reaction A mixture of 10 drops of acetic acid, 1ml ethanol and 5 drops of conc. was warmed over a water bath for 2 minutes. The odor of the ester formed was noted. In another test tube, a mixture of 0.5ml 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 paraffin wax and was shook for several minutes. An odor of the formed ester and a formation of two layers were noted. C. 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 water. The formation of a precipitate was noted. D. 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 a 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 deep burgundy precipitate was observed.

nucleophile and breaking of the s bond to the leaving group. An intermediate product, which is an alkoxide ion, normally forms as and the intermediate formed is protonated to give an alcohol. Involving carboxylic acid derivatives the intermediate forms expels a living group to give a new carbonyl compound. These differences in behaviors towards the reaction are primarily because of their difference in structure. The rate of the overall reaction involves the addition step and the elimination step. The addition step is usually the rate determining step because it is the slowest step involved. Acyl chlorides are the most electron poor and have the withdrawing effect making it the most reactive compound. Also it has the strongest leaving group. With these conditions, amides are the least reactive compounds because they are electron rich and has the weakest leaving group. . Reactions involving carboxylic acid derivatives include hydrolysis, alcoholysis, aminolysis, reduction and Grignard reaction. Hydrolysis is the addition of water to form carboxylic acids. The reaction is as follows:

RESULTS AND DISCUSSION

A. Hydrolysis of Acid Derivatives A white precipitate was observed an no evolution of gas with the addition of AgNO3 to acetyl chloride. For acetic anhydride, no precipitate but an evolution of gas was observed. For ethyl acetate, with the addition of NaOH an alcoholic sent was observed and the disappearance of the odor as it was neutralized with HCl. Wit benzanamide, addition of NaOH and heat yielded an evolution of gas and the red litmus paper turned blue indicating that the solution is basic. B. Alcoholysis: Schotten-Baumann Reaction A fruity odor with a solution with layers was observed when 0.5ml of ethanol, 1ml of water and 0.2ml of acetyl chloride was prepared, with the addition of 20% NaOH solution. C. Aminolysis: Anilide Formation The addition of 0.5ml aniline to the sample yielded a wite crystalline precipitate indicating the presence of acetanilide. D. Hydroxamic Acid Test The preliminary test was no longer performed because the reagents used in this experiment were already given. Doing a preliminary test will surely yield a positive result for the two reagents. For the actual test, both ethyl acetate and acetamide yielded a deep burgundy precipitate which was an indication of a positive result. Carboxylic acids and derivatives involve nucleophilic acyl substitution reaction which is the substitution of the electronegative atom by a nucleophile occurs. The reaction is termed because of its similarity with the reaction of aldehydes and ketones but their difference is seen in that of the product. This reaction involves two events, the formation of the new s bond to the Alcoholysis is the reaction with an alcohol to yield an ester. The reaction is as follows:

Aminolysis is the reaction with ammonia or amine to yield an amide. The reaction is as follows:

Gringard reaction is the reaction of an organomagnesium reagent to yield an alcohol. Esters are also the ones involved here converting them into tertiary alcohols. The reaction is as follows:

Reduction is the reaction with hydride reducing agent to yield an alcohol. Esters are usually involved here which has a primary alcohol as a product. The reaction is as follows:

REFERENCES
(1)McMichael, K., Carboxylic Acid Derivatives

http://chemistry2.csudh.edu/rpendarvis/carboxder.htm ll 9/22/13
(2)Hunt, I., Reactivity of Carboxylic Acid Derivatives

http://www.chem.ucalgary.ca/courses/350/Carey5th/C h20/ch20-1-3.html 9/22/13

(3)Hunt, I., Overveiw of Nucleophilic Acyl Substitution http://www.chem.ucalgary.ca/courses/351/Carey5th/C h20/ch20-2-1.html 9/22/13