1. 18 18-1 © 2003 Thomson Learning, Inc. All rights reserved General, Organic, and Biochemistry, 7e Bettelheim, Brown, and March

2. 18 18-2 © 2003 Thomson Learning, Inc. All rights reserved Chapter 18 Carboxylic Acids, Anhydrides, Esters, and Amides Carboxylic Acids, Anhydrides, Esters, and Amides

3. 18 18-3 © 2003 Thomson Learning, Inc. All rights reserved Introduction In this chapter, we study carboxylic acids, another class of organic compounds containing the carbonyl group we also study three classes of compounds derived from carboxylic acids; anhydrides, esters, and amides each is related to a carboxyl group by loss of H 2 O

4. 18 18-4 © 2003 Thomson Learning, Inc. All rights reserved Carboxylic Acids carboxyl group The functional group of a carboxylic acid is a carboxyl group, which can be represented in any one of three ways

5. 18 18-5 © 2003 Thomson Learning, Inc. All rights reserved Nomenclature IUPAC names for an acyclic carboxylic acid, take longest carbon chain that contains the carboxyl group as the parent alkane e oic aciddrop the final -e from the name of the parent alkane and replace it by -oic acid number the chain beginning with the carbon of the carboxyl group because the carboxyl carbon is understood to be carbon 1, there is no need to give it a number

6. 18 18-6 © 2003 Thomson Learning, Inc. All rights reserved Nomenclature in these examples, the common name is given in parentheses an -OH substituent is indicated by the prefix hydroxy-; an -NH 2 substituent by the prefix amino-

7. 18 18-7 © 2003 Thomson Learning, Inc. All rights reserved Nomenclature dioic acidto name a dicarboxylic acid, add the suffix -dioic acid to the name of the parent alkane that contains both carboxyl groups the numbers of the carboxyl carbons are not indicated because they can be only at the ends of the chain

8. 18 18-8 © 2003 Thomson Learning, Inc. All rights reserved

9. 18 18-9 © 2003 Thomson Learning, Inc. All rights reserved Nomenclature for common names, use, the Greek letters alpha (  ), beta (  ), gamma (  ), and so forth to locate substituents

10. 18 18-10 © 2003 Thomson Learning, Inc. All rights reserved 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

11. 18 18-11 © 2003 Thomson Learning, Inc. All rights reserved Physical Properties carboxylic acids have significantly higher boiling points than other types of organic compounds of comparable molecular weight their higher boiling points 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

12. 18 18-12 © 2003 Thomson Learning, Inc. All rights reserved Physical Properties carboxylic acids are more soluble in water than are alcohols, ethers, aldehydes, and ketones of comparable molecular weight

13. 18 18-13 © 2003 Thomson Learning, Inc. All rights reserved Acidity of RCOOH Carboxylic acids are weak acids values of K a for most unsubstituted aliphatic and aromatic carboxylic acids fall within the range 10 -4 to 10 -5 (pK a 4.0 - 5.0)

14. 18 18-14 © 2003 Thomson Learning, Inc. All rights reserved Acidity of RCOOH substituents of high electronegativity, especially -OH, - Cl, and -NH 3 +, near the carboxyl group increase the acidity of carboxylic acids both dichloroacetic acid and trichloroacetic acid are stronger acids than H 3 PO 4 (pK a 2.1)

15. 18 18-15 © 2003 Thomson Learning, Inc. All rights reserved Reaction With Bases All carboxylic acids, whether soluble or insoluble in water, react with NaOH, KOH, and other strong bases to form water-soluble salts they also form water-soluble salts with ammonia and amines

16. 18 18-16 © 2003 Thomson Learning, Inc. All rights reserved Reaction With Bases like inorganic acids, carboxylic acids react with sodium bicarbonate and sodium carbonate to form water- soluble sodium salts and carbonic acid carbonic acid then decomposes to give water and carbon dioxide, which evolves as a gas

17. 18 18-17 © 2003 Thomson Learning, Inc. All rights reserved Ionization versus pH The form in which a carboxylic acid exist in an aqueous solution depends on the solution’s pH

18. 18 18-18 © 2003 Thomson Learning, Inc. All rights reserved Anhydrides anhydride The functional group of an anhydride is two carbonyl groups bonded to the same oxygen the anhydride may be symmetrical (from two identical acyl groups), or mixed (from two different acyl groups) acid anhydrideto name an anhydride, drop the word "acid" from the name of the carboxylic acid from which the anhydride is derived and add the word "anhydride"

19. 18 18-19 © 2003 Thomson Learning, Inc. All rights reserved Esters ester The functional group of an ester is a carbonyl group bonded to an -OR group both IUPAC and common names of esters are derived from the names of the parent carboxylic acids ic acidatename the alkyl or aryl group bonded to oxygen first, followed by the name of the acid; replace the suffix -ic acid by -ate lactonea cyclic ester is called a lactone

20. 18 18-20 © 2003 Thomson Learning, Inc. All rights reserved Amides amide The functional group of an amide is a carbonyl group bonded to a nitrogen atom oic acid ic acid amideto 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-

21. 18 18-21 © 2003 Thomson Learning, Inc. All rights reserved Amides lactama cyclic amide is called a lactam the penicillins are referred to as  -lactam antibiotics

22. 18 18-22 © 2003 Thomson Learning, Inc. All rights reserved Amides the cephalosporins are also  -lactam antibiotics

23. 18 18-23 © 2003 Thomson Learning, Inc. All rights reserved Fischer Esterification Fischer esterification Fischer esterification is one of the most commonly used preparations of esters in Fischer esterification, a carboxylic acid is reacted with an alcohol in the presence of an acid catalyst, such as concentrated sulfuric acid Fischer esterification is reversible it is possible to drive it in either direction by the choice of experimental conditions (Le Chatelier’s principle)

24. 18 18-24 © 2003 Thomson Learning, Inc. All rights reserved Fischer Esterification in Fischer esterification, the alcohol adds to the carbonyl group of the carboxylic acid to form a tetrahedral carbonyl addition intermediate the intermediate then loses H 2 O to give an ester

25. 18 18-25 © 2003 Thomson Learning, Inc. All rights reserved Preparation of Amides In principle, we can form an amide by treating a carboxylic acid with an amine and removing -OH from the acid and an -H from the amine in practice what occurs if the two are mixed is an acid- base reaction to form an ammonium salt if this salt is heated to a high enough temperature, water is eliminated and an amide forms

26. 18 18-26 © 2003 Thomson Learning, Inc. All rights reserved Preparation of Amides it is much more common to prepare amides by treating an amine with an anhydride

27. 18 18-27 © 2003 Thomson Learning, Inc. All rights reserved Hydrolysis of Anhydrides carboxylic anhydrides, particularly the low-molecular- weight ones, react readily with water to give two carboxylic acids

28. 18 18-28 © 2003 Thomson Learning, Inc. All rights reserved Hydrolysis of Esters esters hydrolyze only 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 a large excess of water drives the equilibrium to the right to form the carboxylic acid and alcohol (Le Chatelier's principle)

29. 18 18-29 © 2003 Thomson Learning, Inc. All rights reserved Hydrolysis of Esters we can also hydrolysis of an ester using a hot aqueous base, such as aqueous NaOH saponificationthis reaction is often called saponification, a reference to its use in the manufacture of soaps the carboxylic acid formed in the hydrolysis reacts with hydroxide ion to form a carboxylic acid anion each mole of ester hydrolyzed requires one mole of base

30. 18 18-30 © 2003 Thomson Learning, Inc. All rights reserved Hydrolysis of Amides amides require more vigorous conditions for hydrolysis in both acid and base than do esters hydrolysis in hot aqueous acid gives a carboxylic acid and an ammonium ion 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

31. 18 18-31 © 2003 Thomson Learning, Inc. All rights reserved 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

32. 18 18-32 © 2003 Thomson Learning, Inc. All rights reserved Phosphoric Anhydrides phosphoric anhydridethe functional group of a phosphoric anhydride is two phosphoryl (P=O) groups bonded to the same oxygen atom

33. 18 18-33 © 2003 Thomson Learning, Inc. All rights reserved Phosphoric Esters phosphoric acid forms mono-, di-, and triphosphoric esters in more complex phosphoric 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

34. 18 18-34 © 2003 Thomson Learning, Inc. All rights reserved Step-Growth Polymers 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

35. 18 18-35 © 2003 Thomson Learning, Inc. All rights reserved Polyamides Nylon-66 Nylon-66 was the first purely synthetic fiber it is synthesized from two six-carbon monomers

36. 18 18-36 © 2003 Thomson Learning, Inc. All rights reserved Polyamides Kevlarthe polyaromatic amide known as Kevlar is also made from aa aromatic dicarboxylic acid and an aromatic diamine

37. 18 18-37 © 2003 Thomson Learning, Inc. All rights reserved Polyesters the first polyester involved polymerization of this diacid and ethylene glycol

38. 18 18-38 © 2003 Thomson Learning, Inc. All rights reserved Polycarbonates polycarbonateLexan, the most familiar polycarbonate, is formed by reaction between the disodium salt of bisphenol A and phosgene

39. 18 18-39 © 2003 Thomson Learning, Inc. All rights reserved End Chapter 18