1. Carboxylic Acids, Anhydrides, Esters, and Amides
Chapter 17
Carboxylic Acids, Anhydrides, Esters, and Amides

2. Introduction
Carboxylic acids, another carbonyl containing functional group
also anhydrides, esters, and amides
loss of H2O is commonality here

3. Carboxylic Acids
The functional group of a carboxylic acid is a carboxyl group, which can be represented in any one of three ways

4. Nomenclature IUPAC names
Find the longest carbon chain that contains the carboxyl group as the parent alkane
drop the final -e and replace it by -oic acid
carboxyl group is carbon 1
because the carboxyl carbon is understood to be carbon 1, there is no need to give it a number

5. Nomenclature
in these examples, the common name is given in parentheses
an -OH substituent is indicated by the prefix hydroxy-; an -NH2 substituent by the prefix amino-

6. Nomenclature
dicarboxylic acids have the suffix -dioic acid and the parent contains both carboxyl groups
the numbers of the carboxyl carbons are not indicated

8. Nomenclature
for common names, use, the Greek letters alpha (a), beta (b), gamma (g), and so forth to locate substituents

9. Physical Properties
The carboxyl group contains three polar covalent bonds; C=O, C-O, and O-H
the polarity of these bonds determines the major physical properties of carboxylic acids

10. Physical Properties carboxylic acids have high boiling points
these are a result of their polarity and the fact that hydrogen bonding between two carboxyl groups creates a dimer that behaves as a higher-molecular-weight compound

11. Physical Properties
carboxylic acids are more soluble in water than are alcohols, ethers, aldehydes, and ketones of comparable molecular weight

12. Acidity of RCOOH The hydrogen on the oxygen is acidic
substituents of high electronegativity, especially -OH, -Cl, and -NH3+, near the carboxyl group increase the acidity

13. Reaction With Bases
All carboxylic acids react with NaOH, KOH, and other strong bases to form water-soluble salts
they also form water-soluble salts with ammonia and amines

14. Ionization versus pH
The form in which a carboxylic acid exist in an aqueous solution depends on the solution’s pH

15. Anhydrides
The anhydride is two carbonyl groups bonded to the same oxygen
The most common are symmetrical but the mixed anhydride may be made.
to name an anhydride, drop the word "acid" and add the word "anhydride"

16. Esters The ester is a carbonyl group bonded to an -OR group
esters names are derived from the names of the parent carboxylic acids
name the “R” first, followed by the name of the acid; replace the suffix -ic acid by -ate
a cyclic ester is called a lactone

17. Amides
The functional group of an amide is a carbonyl group bonded to a nitrogen atom
to name an amide, drop the suffix -oic acid from the IUPAC name of the parent acid, or -ic acid from its common name, and add -amide
if the amide nitrogen is bonded to an alkyl or aryl group, name the group and show its location on nitrogen by N- ; two alkyl or aryl groups by N,N-di-

18. Amides a cyclic amide is called a lactam
the penicillins are referred to as b-lactam antibiotics

19. Amides
the cephalosporins are also b-lactam antibiotics

20. Fischer Esterification
one of the most commonly used preparations of esters
carboxylic acid reacted with an alcohol in the presence of an acid catalyst
reversible

21. Preparation of Amides
If a carboxylic acid and an amine are mixed, an acid-base reaction to form an ammonium salt results
if this salt is heated to a high enough temperature, water is eliminated and an amide forms

22. Preparation of Amides
it is much more common to prepare amides by treating an amine with an anhydride

23. Hydrolysis of Anhydrides
carboxylic anhydrides, particularly the low-molecular- weight ones, react readily with water to give two carboxylic acids

24. Hydrolysis of Esters
esters hydrolyze very slowly, even in boiling water
hydrolysis becomes considerably more rapid, however, when the ester is heated in aqueous acid or base
hydrolysis of esters in aqueous acid is the reverse of Fischer esterification

25. Hydrolysis of Esters
hydrolysis of an ester using a hot aqueous base can also work – but not a catalyst here!
this reaction is often called saponification, a reference to its use in the manufacture of soaps
the carboxylic acid formed reacts with hydroxide ion
each mole of ester hydrolyzed requires one mole of base

26. Hydrolysis of Amides amides require more vigorous conditions
hydrolysis in hot aqueous acid is not catalytic
hydrolysis is driven to completion by the acid-base reaction between ammonia or the amine and the acid to form an ammonium ion
each mole of amide requires one mole of acid

27. Hydrolysis of Amides
hydrolysis of an amide in aqueous base gives a carboxylic acid salt and ammonia or an amine
hydrolysis is driven to completion by the acid-base reaction between the carboxylic acid and base to form a salt
each mole of amide requires one mole of base

28. Phosphoric Anhydrides
the functional group of a phosphoric anhydride is two phosphoryl (P=O) groups bonded to the same oxygen atom

29. Phosphoric Esters
phosphoric acid forms mono-, di-, and triphosphoric esters
it is common to name the organic molecule and then indicate the presence of the phosphoric ester by either the word "phosphate" or the prefix phospho-
dihydroxyacetone phosphate and pyridoxal phosphate are shown as they are ionized at pH 7.4, the pH of blood plasma

30. Step-Growth Polymers
Step-growth polymers are formed by reaction between molecules containing two functional groups, with each new bond created in a separate step
in this section, we discuss three types of step-growth polymers; polyamides, polyesters, and polycarbonates

31. Polyamides Nylon-66 was the first purely synthetic fiber
it is synthesized from two six-carbon monomers

32. Polyamides
the polyaromatic amide known as Kevlar is also made from aa aromatic dicarboxylic acid and an aromatic diamine

33. Polyesters
the first polyester involved polymerization of this diacid and ethylene glycol

34. Polycarbonates
Lexan, the most familiar polycarbonate, is formed by reaction between the disodium salt of bisphenol A and phosgene

35. Chapter 18
End
Chapter 18