1. Carboxylic Acids And Their Derivatives
Dr Nahed Elsayed 1

2. Learning Objectives
Chapter nine introduces carboxylic acids and their derivatives. The chemistry is very similar to that of aldehydes and ketones because of the presence of the carbonyl group . The main topics in this chapter that the students should know and understand include:
The structure of carboxylic acids
The common and IUPAC nomenclature of carboxylic acids
The physical properties of carboxylic acids
The Factors affecting acidity of carboxylic acids.
The different ways to make carboxylic acids
Salt formation reactions of carboxylic acids
The nucleophilic substitution reactions at the carbonyl carbon and the specific products formed in each case.
The chemistry of carboxylic acid derivatives

3. 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 –CO2H or –COOH
Carboxylic acids are classified as aliphatic R-COOH or aromatic Ar-COOH depending on the group bonded to the carboxylic group.
The simplest aliphatic acid is formic acid R= H
The fatty acid is long chain aliphatic acids CH3-(CH2)16-COOH

4. Nomenclature Of Carboxylic Acids
Common Nomenclature
Some carboxylic acids are called after characteristic properties or their origin.
All common names ending -ic acid
Formula Common name origin of name
HCOOH formic acid Latin for ant
CH3COOH acetic acid Latin for vinegar
CH3CH2COOH propionic acid Greek for milk
CH3 (CH2)2COOH butyric acid Latin for butter
CH3 (CH2)3COOH valeric acid valerian root
The positions 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), etc.

5. Example of dicarboxylic acids
Succinic acid
Some aromatic acids have common names

6. IUPAC Nomenclature
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
If there are substituents identify their names, positions and list them as prefixes in alphabetical order.
Examples: (CH3)2CH - CH(CH3) - CH2 - CH2 - COOH is called
4,5-Dimethylhexanoic acid
Butanoic acid
Pentanoic acid

7. 3-Aminobutanoic acid
1,4-Butandioic acid
3-Bromo-2-hydroxy-4-hexenoic acid
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.

8. Some aromatic compounds have common names accepted by the IUPAC also they can be named as benzene carboxylic acids

9. Physical Properties OF Carboxylic Acids
Solubility
Carboxylic acids are polar, they can form hydrogen bonds with water molecules
The first four aliphatic acids are completely miscible in water. Higher members are less soluble
Aromatic acids are insoluble in water

10. Boiling Points M.F. M.W bp / °C Propanol C3H8O 60.01 97.2
Carboxylic acids have exceptionally high boiling points than alcohols and aldehydes, because their dimeric structures. of identical relative molecular masses, For example:
M.F. M.W bp / °C
Propanol C3H8O
Ethanoic acid C2H4O
Hydrogen-bonded acid dimer

11. Acid Strength
Carboxylic acids are stronger acids compared to alcohols and phenols
Electron withdrawing substituents near the carboxyl group increase the acidity
Whereas electron donating substituents decrease the acidity .
HCOOH > CH3COOH > CH3CH2COOH > CH3CH2CH2CH2COOH ( size of R group)
Cl3CCOOH > Cl2CHCOOH > ClCH2COOH > CH3COOH ( number of electron withdrawing atoms) 11

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

13. 3- Carbonation Of Grignard Reagents 4- Hydrolysis Of Nitriles

14. Reactions Of Carboxylic Acids
1- Salts Formation

15. 2- Substitution Of Hydroxyl Group
General Equation
Examples

16. Carboxylic Acid Derivatives
Acid Chloride Ester Amide Acid anhydride
The derivatives of carboxylic acids are compounds in which the -OH of carboxylic acid is replaced by nucleopile (-X for acid halide, -OR for ester, -NH2, -NHR, -NR2 for amids, -OOCR for anhydride).
Carboxylic acids derivatives can converted to carboxylic acids by simple acidic or basic hydrolysis.

17. Carboxylic Acid Derivatives
1-Nomenclature Of Acid Chlorides
Replace the -ic acid ending in the name of the parent acid by –yl chloride
IUPAC: Ethanoyl chloride Benzoylchloride Propanoyl chloride
Common : Acetyl chloride

18. (IUPAC) Ethyl ethanoate Methyl benzoate
2- Nomenclature of esters
The alkyl group (R’) is written first followed by the name of the parent acid with replacing of the ending –ic acid by –ate :
(IUPAC) Ethyl ethanoate Methyl benzoate
(common) Ethyl acetate
(IUPAC) Methyl propanoate Isopropyl-4-hydroxy-5-methyl-5- hexenoate

19. 3- Nomenclature of amide
Replace the ending oic acid of the parent acid’s by the word amide
If there is R group on the nitrogen atom, it is listed first and designated with –N
(IUPAC) Ethanamide Benzamide N-Methylpropanamide
(common) Acetamide N-Methylpropionamide
(IUPAC) N,N-Dimethylmethamide N-Ethyl-N-methylbenzamide
(Common) N,N-Dimethylformamide

20. 4- Nomenclature of anhydride
An anhydride is named by replacing the word acid in the corresponding acid by the word anhydride. Due to it is obtained from corresponding acid by dehydration as shown in the following equation:
(IUPAC) Ethanoic anhydride Benzoic anhydride Butandioic anhydride
(Common) Acetic anhydride Succinic anhydride

22. Reaction of Derivatives of carboxylic acid
On hydrolysis (reaction with H2O/ H+) all carboxylic acid derivatives convert to carboxylic acid.

23. Questions 1- Reaction of with CO2 under heat and pressure gives:
2- Oxidation of C6H5CH2OH with KMnO4 gives:

24. 3- The most acidic compound is?
4- The common name of this compound is?
A) N,N-Dimethylacetamide B) N,N-Dimethyl propanamide
C) N,N-Dimethylpropionamide D) N,N-Dimethylbutanamide
5- Acid halide react with ammonia to give?
A) Amines B)Amides C) Phenols D) Alcohols

25. Thank You for your kind attention !
Questions?