1. Carboxylic Acids and Their Derivatives By: Dr. Shatha Alaqeel

2. 2 Structure Of Carboxylic Acids Carboxylic acids are organic acids contain one or more carboxyl group A carboxyl group is made up of a carbonyl (C=O) group and a hydroxyl (O-H) group It is often written in condensed form as –CO 2 H or –COOH The general formula of a carboxylic acid is R-COOH or Ar-COOH

3. Nomenclature of Carboxylic Acid General formula: R-COOH or Ar-COOH Find the longest continuous carbon chain contains the COOH group to get the root name of the parent hydrocarbon, then replace the ending -e by the suffix –oic acid. In the IUPAC: Find the longest continuous carbon chain contains the COOH group to get the root name of the parent hydrocarbon, then replace the ending -e by the suffix –oic acid. Number the chain starting with the carbon of COOH group as C-1 Number the chain starting with the carbon of COOH group as C-1 If there are substituents identify their names, positions and list them as prefixes in alphabetical order. If there are substituents identify their names, positions and list them as prefixes in alphabetical order. common Formic acid Acetic acid Propionic acid Butyric acid Valeric acid IUPAC Methanoic acid Ethanoic acid Propanoic acid Butanoic acid Pentanoic acid

4. α indicating the carbon atom next to COOH group (C2), β (C3), γ (C4), δ (C5), etc. In common : the position of the carbons present on the acid chain, are located by the Greek letters α indicating the carbon atom next to COOH group (C2), β (C3), γ (C4), δ (C5), etc. In IUPAC: The carboxylic carbon is numbered 1. common:  -  - Dimethyl butyric acid IUPAC: 2,3-Dimethyl butanoic acid

5. 5 Cyclic compounds containing one or more COOH groups attached to the ring are named by identifying the name of the ring followed by the word carboxylic acid or dicarboxylic acids etc. The carbon atom bearing the carboxylic group is numbered 1 and the substituents are numbered relative to it. Cyclopropane Cyclobutane Cyclopentane Cyclohexane Carboxylic acid Carboxylic acid Carboxylic acid Carboxylic acid

6. common common Benzoic acid Salicylic acid IUPAC IUPAC Benzene carboxylic acid 2-Hydroxybenzenecarboxylic acid common common Phethalic acid Terephtalic acid IUPAC IUPAC Benzene-1,2-dicarboxylic acid Benzene-1,4-dicarboxylic acid Some aromatic compounds have common names accepted by the IUPAC also they Can be named as benzene carboxylic acids Can be named as benzene carboxylic acids

7. Physical Properties OF Carboxylic Acids Solubility Carboxylic acids are polar, they can form hydrogen bonds with water molecules Smaller carboxylic acids (1 to 4 carbons) are soluble in water Smaller carboxylic acids (1 to 4 carbons) are soluble in water Whereas the solubility of bigger carboxylic acids decrease with size Whereas the solubility of bigger carboxylic acids decrease with size Aromatic acids are insoluble in water Aromatic acids are insoluble in water

8. The boiling points of carboxylic acids indicate a greater degree than alcohols This is due to carboxylic acids usually exist as dimeric pairs by forming two intramolecular hydrogen bonds in nonpolar media This is due to carboxylic acids usually exist as dimeric pairs by forming two intramolecular hydrogen bonds in nonpolar media Boiling Points

9. Carboxylic acids are the most acidic simple organic compounds (they are stronger acids by over ten powers of ten compared to alcohols of comparable weights); also they are more acidic than phenols Carboxylic acids are the most acidic simple organic compounds (they are stronger acids by over ten powers of ten compared to alcohols of comparable weights); also they are more acidic than phenols However, they are weak acids compared to inorganic acids (HCl or H 2 SO 4 ) However, they are weak acids compared to inorganic acids (HCl or H 2 SO 4 ) Adjacent electron withdrawing substituents near the carboxyl group increase the acidity Adjacent electron withdrawing substituents near the carboxyl group increase the acidity Whereas electron donating substituents decrease the acidity. Whereas electron donating substituents decrease the acidity. 9 HCOOH > CH 3 COOH > CH 3 CH 2 COOH > CH 3 CH 2 CH 2 CH 2 COOH ( size of R group) HCOOH > CH 3 COOH > CH 3 CH 2 COOH > CH 3 CH 2 CH 2 CH 2 COOH ( size of R group) Cl 3 CCOOH > Cl 2 CHCOOH > ClCH 2 COOH > CH 3 COOH > (OCH 3 )CH 2 COOH ( number of e.w.g. and e.d. g.) ( position of e.w.g. relative to COOH group) CH 3 CH 2 CH 2 CH(Cl)COOH > CH 3 CH 2 CH(Cl)CH 2 COOH > CH 3 CH(Cl)CH 2 CH 2 COOH > CH 2 (Cl)CH 2 CH 2 CH 2 COOH ( position of e.w.g. relative to COOH group) Acidity And Acid Strength

10. 1- Oxidation Of Primary Alcohols 1- Oxidation Of Primary Alcohols 2- Oxidation Of Alkyl Benzenes 2- Oxidation Of Alkyl Benzenes Preparation Of Carboxylic acids

11. 3- Carbonation Of Grignard Reagents 3- Carbonation Of Grignard Reagents 4- Hydrolysis Of Nitriles 4- Hydrolysis Of Nitriles

12. Reactions of Carboxylic Acids 1- Salts Formation

13. 2- Substitution of hydroxyl group

14. Carboxylic Acid Derivatives Acid Chloride Ester Amide acid anhydride 1-Nomenclature of acid chloride ٌ Replacing the –ic acid ending of the parent acid by –yl chloride: Ethanoyl chloride Benzoyl chloride Acetyl chloride

15. 2- Nomenclature of esters The alkyl group (R’) is named first followed by the name of the parent acid with the ending –ate in place –ic acid: Ethyl ethanoate Methyl benzoate Ethyl acetate

16. 3- Nomenclature of amide Replacing the ending oic acid of the parent acid’s by amide Ethanamide Benzamide Acetamide N,N-Dimethylmethamide N-Ethyl-N-methylbenzamide N,N-Dimethylformamide

17. 4- Nomenclature of anhydride An anhydride is named by replacing the word acid by anhydride. Ethanoic anhydride Benzoic anhydide Succinic anhydride

18. Reaction of Esters

19. Acid Chlorides: Reactions

20. Acid anhydride: Reactions

21. Reactions of Amides