1. Chapter 11
Reactions of Carboxylic Acids and Carboxylic Acid Derivatives
Paula Yurkanis Bruice
University of California,
Santa Barbara

2. Contents of Chapter 11 Naming Carboxylic Acids and Derivatives
Physical Properties of Carbonyl Compounds
Reactivity of Carboxylic Acid Derivatives
Reactions of Carboxylic Acids and Derivatives
Chapter 11

3. IUPAC Nomenclature of Carboxylic Acids
Select as the parent compound the longest chain of carbon atoms that contains the carboxyl group
Change the suffix –e of the parent name to –oic acid
Carboxyl carbon is carbon 1
Chapter 11

4. Examples
Chapter 11

5. Dicarboxylic Acids
Dicarboxylic acids are named by adding the suffix –dioic acid to the name of the parent compound that contains both carboxyl groups
Chapter 11

6. Examples
Chapter 11

7. Aromatic Carboxylic Acids
Chapter 11

8. Derivatives of Carboxylic Acids
Chapter 11

9. Nomenclature
Acid chlorides are named by replacing the –ic acid of the carboxylic acid with –yl chloride.
Chapter 11

10. Nomenclature
Anhydrides are named by adding the word anhydride to the name of the parent acid.
Chapter 11

11. Nomenclature
Esters are named as a derivative of the carboxylic acid from which it is derived.
The alkyl or aryl group attached to the oxygen is named first.
Chapter 11

12. Nomenclature
Chapter 11

13. Nomenclature
Amides are named as derivatives of their carboxylic acid by dropping the suffix of the acid and adding –amide.
Note: the above amides are all primary (1o) amides.
Chapter 11

14. Nomenclature
If a hydrogen atom of an amide is replaced by an alkyl or aryl group, the substituent is named and its location on nitrogen indicated by N- (or N,N- if there are two groups)
Chapter 11

15. Physical Properties of Carboxylic Acids
Carboxylic acids can form H-bonding molecule pairs, so the boiling points of carboxylic acids are somewhat higher than even alcohols with the same molar mass because they often boil away from the liquid as molecule pairs:
Chapter 11

16. Physical Properties of Carboxylic Acids
Chapter 11

17. Physical Properties of Amides
Hydrogen bonding is possible.
Chapter 11

18. Acidity of Carboxylic Acids
All carboxylic acids, whether soluble or insoluble in water, react quantitatively with NaOH, KOH, and other strong bases to form salts
Chapter 11

19. Preparation of Esters
A carboxylic acid can be converted to an ester by heating with an alcohol in the presence of an acid catalyst, usually concentrated sulfuric acid.
Chapter 11

20. Stabilities of Carboxylic Acid Derivatives
In principle carboxylic acid derivatives should be able to be interconverted into one another using a scheme like the one shown below
In the scheme below LG represents the original group, like OR, attached to the starting compound (OR would make this an ester)
Nu (nucleophile) forces LG (leaving group) to leave and replaces it, making a new compound
In this scheme if Nu is amine and LG is alkoxy (OR) then an ester is converted into an amide
Chapter 11

21. Stabilities of Carboxylic Acid Derivatives
Scheme on previous slide will only work if Nu is less stable than LG, so reaction goes downhill
Relative energy of Nu or LG given by pKa of conjugate acid
In table below the derivatives at the top are less stable than those beneath
In neutral or basic media you can convert a derivative higher up into one lower down, but not vice-versa
Chapter 11

22. Stabilities of Carboxylic Acid Derivatives
In acidic media interconversion of carboxylic acid derivatives works by a different mechanism
In this mechanism LG can be protonated before it leaves
In this case the leaving group is no longer negatively charged when it leaves; therefore it leaves more easily (more stable)
In acidic media you can interconvert any of the carboxylic acid derivatives into one another
Chapter 11

23. Reactions Carboxylic Acid Derivatives
To work out the product of a carboxylic acid derivative reaction first make sure the reaction will work
If the reaction is done in acid or goes from a less stable derivative to a more stable derivative polarize the most polar bonds in the reactants and swap partners
Always polarize the carbonyl carbon positive and the leaving group negative in these reactions
Chapter 11