Chapter 17

Carboxylic Acids,
Anhydrides, Esters,
and Amides
Introduction
 Carboxylic acids, another carbonyl
containing functional group
 also anhydrides, esters, and amides
 loss of H2O is commonality here
O O O O O
RCOH RCOCR' RCOR' RCNH2
A carboxylic acid An anhydride An ester An amide
O O O O
RC-OH H-OCR' RC-OH H-OR' RC-OH H-NH2
Carboxylic Acids

 The functional group of a carboxylic acid

is a carboxyl group,
group which can be
represented in any one of three ways
O
C-OH COOH CO2 H
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
Nomenclature
 in these examples, the common name is
given in parentheses
O O
1 3 1
6
OH OH
Hexanoic acid 3-Methylbutanoic acid
(Caproic acid) (Isovaleric acid)

 an -OH substituent is indicated by the prefix

hydroxy-; an -NH2 substituent by the prefix
amino- 5OH 1
O
HN COOH
2
OH
5-Hydroxyhexanoic acid 4-Aminobenzoic acid
Nomenclature
 dicarboxylic acids have the suffix - dioic acid and
the parent contains both carboxyl groups
 the numbers of the carboxyl carbons are not
O O O
indicated HO 2 1 3 1
OH HO OH
O
Ethanedioic acid Propanedioic acid
(Oxalic acid) (Malonic acid)

O O O O
1 5 1 HO 1
HO 4 6
OH HO OH OH
O O
Butanedioic acid Pentanedioic acid Hexanedioic acid
(Succinic acid) (Glutaric acid) (Adipic acid)
 IUPAC Name Common
Structure (acid) Name Derivation
HCOOH methanoic formic Latin: formica, ant
CH3 COOH ethanoic acetic Latin: acetum, vinegar
CH3 CH2 COOH propanoic propionic Greek: propion, first fat
CH3 (CH2 ) 2 COOH butanoic butyric Latin: butyrum, butter
CH3 (CH2 ) 3 COOH pentanoic valeric Latin: valere, to be strong
CH3 (CH2 ) 4 COOH hexanoic caproic Latin: caper, goat
CH3 (CH2 ) 6 COOH octanoic caprylic Latin: caper, goat
CH3 (CH2 ) 8 COOH decanoic capric Latin: caper, goat
CH3 (CH2 ) 1 0 COOH dodecanoic lauric Latin: laurus, laurel
CH3 (CH2 ) 1 2 COOH tetradecanoic myristic Greek: myristikos, fragrant
CH3 (CH2 ) 1 4 COOH hexadecanoic palmitic Latin: palma, palm tree
CH3 (CH2 ) 1 6 COOH octadecanoic stearic Greek: stear, solid fat
CH3 (CH2 ) 1 8 COOH eicosanoic arachidic Greek: arachis, peanut
Nomenclature
 for common names, use, the Greek letters
alpha (), beta (), gamma (), and so forth
to locate substituents

O O
4
O
3 2 1 1 2
C-C-C-C-OH H2 N 4  OH
    OH
OH
4-Aminobutanoic acid 2-Hydroxypropanoic acid
(-Aminobutyric acid; GABA) (-Hydroxypropionic acid;
lactic acid)
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
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
hydrogen bonding - +
between two O H O
molecules
H3 C C C CH3
O H O
+ -
Physical Properties
 carboxylic acids are more soluble in water
than are alcohols, ethers, aldehydes, and
ketones of comparable molecular weight
Boiling
Molecular Point Solubility
Structure Name Weight (°C) (g/100 mL H2O)
CH3 COOH acetic acid 60.5 118 infinite
CH3 CH2 CH2 OH 1-propanol 60.1 97 infinite
CH3 CH2 CHO propanal 58.1 48 16
CH3 (CH2 ) 2 COOH butanoic acid 88.1 163 infinite
CH3 (CH2 ) 3 CH2 OH 1-pentanol 88.1 137 2.3
CH3 (CH2 ) 3 CHO pentanal 86.1 103 slight
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

Formula: CH3 COOH ClCH2 COOH Cl2 CHCOOH Cl3 CCOOH

Name: Acetic Chloroacetic Dichloroacetic Trichloroacetic
acid acid acid acid
pK a: 4.76 2.86 1.48 0.70
Increasing acid strength
Reaction With Bases
 All carboxylic acids react with NaOH,
KOH, and other strong bases to form
water-soluble salts
H2 O - +
COOH + NaOH COO Na + H2 O

Benzoic acid Sodium benzoate

(slightly soluble in water) (60 g/100 mL water)
 they also form water-soluble salts with
ammonia and amines
H2 O - +
COOH + NH3 COO NH4
Benzoic acid Ammonium benzoate
(slightly soluble in water) (20 g/100 mL water)
Ionization versus pH

 The form in which a carboxylic acid exist

in an aqueous solution depends on the
solution’s pH
O O O O
OH- OH-
R-C-OH + R-C-OH + R-C-O- + R-C-O
-
H H
at pH 2.0 at pH = pK a = 4.0 - 5.0 at pH 8.0
or lower both forms are present in or higher
approximately equal amounts
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"
acid
and add the word "anhydride"
anhydride
O O
CH3 C-O-CCH3
Acetic anhydride
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
O O O
O
CH3 COCH2 CH3 O O O
Ethyl ethanoate Diethyl pentanedioate A five-membered
(Ethyl acetate) (Diethyl glutarate) lactone
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-
O O O
CH3 CNH2 CH3 CNHCH3 HCN(CH3 ) 2
Acetamide N-Methylacetamide N,N-Dimethylformamide
(a 1° amide) (a 2° amide) (a 3° amide)
Amides
 a cyclic amide is called a lactam
O O

 NH NH
A four-membered lactam A seven-membered lactam
(a -lactam)

 the penicillins are referred to as -lactam

The-lactam ring
antibiotics HO
O
N S CH3
The penicillins
differ in the group NH2 H N CH3
O
bonded to the COOH
carbonyl carbon Amoxicillin
Amides
 the cephalosporins are also -lactam
antibiotics
...and the group bonded
to this carbon of the
O six-membered ring
S
The cephalosporins N
differ in the group NH2 H N
O CH3
bonded to the carbonyl
carbon... COOH
Cefalexin
(a -lactam antibiotic)
Fischer Esterification
 one of the most commonly used
preparations of esters
 carboxylic acid reacted with an alcohol in the
presence of an acid catalyst
O H2 SO4 O
CH3 C-OH + H-OCH2 CH3 CH3 COCH2 CH3 + H2 O
Ethanoic acid Ethanol Ethyl ethanoate
(Acetic acid) (Ethyl alcohol) (Ethyl acetate)

 reversible
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
O O +
-
CH3 C-OH + H2 NCH2 CH3 CH3 C-O H3 NCH2 CH3
Acetic Ethanamine An ammonium
acid (Ethylamine) salt
O
heat
CH3 C-NHCH2 CH3 + H2 O
An amide
Preparation of Amides
 it is much more common to prepare amides
by treating an amine with an anhydride

O O O O
CH3 C-O-CCH3 + H2 NCH2 CH3 CH3 C-NHCH2 CH3 + CH3 COH
Acetic anhdyride An amide
Hydrolysis of Anhydrides
 carboxylic anhydrides, particularly the low-
molecular- weight ones, react readily with
water to give two carboxylic acids

O O O O
CH3 COCCH3 + H2 O CH3 COH + HOCCH3
Acetic anhydride Acetic acid Acetic acid
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
O + O
H
CH3 COCH2 CH3 + H2 O CH3 COH + CH3 CH2 OH
Ethyl acetate Acetic acid Ethanol
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,
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
O O
H2 O
CH3 COCH2 CH3 +NaOH CH3 CO-Na + + CH3 CH2 OH
Ethyl acetate Sodium Sodium Ethanol
hydroxide acetate
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

O O
H2 O + -
CH3 CH2 CH2 CNH2 + H2 O + HCl CH3 CH2 CH2 COH + NH4 Cl
he at
Butanamide Butanoic acid
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

O O
H2 O
CH3 CNH + NaOH CH3 CO-Na+ + H2 N
he at
Acetanilide Sodium Aniline
acetate
Phosphoric Anhydrides
 the functional group of a phosphoric anhydride is two
phosphoryl (P=O) groups bonded to the same
oxygen atom
O O O O
- -
HO-P-O-P-OH O-P-O-P-O
- -
OH OH O O
Diphosphoric acid Diphosphate ion
(Pyrophosphoric acid) (Pyrophosphate ion)

O O O O O O
- -
HO-P-O-P-O-P-OH O-P-O-P-O-P-O
OH OH OH O- O- O-
Triphosphoric acid Triphosphate ion
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
CH2 OH CHO O
O CO O HO CH2 O-P-O
-

CH3 O-P-OH CH2 -O-P-O- O-

OCH3 O- H3 C N
Dimethyl phosphate Dihydroxyacetone Pyridoxal phosphate
phosphate
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
Polyamides
 Nylon-66 was the first purely synthetic fiber
 it is synthesized from two six-carbon monomers
remove H2O
O H
HO H N heat
OH + N H
-H2 O
O H
Hexanedioic acid 1,6-Hexanediamine
(Adipic acid) (Hexamethylenediamine)
O H
N
N
n
O H
Nylon-66
(a polyamide)
Polyamides
 the polyaromatic amide known as Kevlar is also
made from aa aromatic dicarboxylic acid and an
aromatic diamine
remove H2O
O O H H
+ N N heat
nHOC COH
H H -H2 O
1,4-Benzenedicarboxylic 1,4-Benzenediamine
acid (p-Phenylenediamine)
(Terephthalic acid)

O O
C CNH NH
n
Kevlar
(a polyaromatic amide)
Polyesters
 the first polyester involved polymerization of this
diacid and ethylene glycol
remove CH3 OH

O OCH3 HO heat
+
CH3 O O OH -CH3 OH
Dimethyl terephthalate 1,2-Ethanediol
(Ethylene glycol)
O O
O
O n
Poly(ethylene terephthalate)
(Dacron, Mylar)
Polycarbonates
 Lexan, the most familiar polycarbonate,
polycarbonate is formed by
reaction between the disodium salt of bisphenol A
and phosgene + -
remove Na Cl

CH3 O
+ -
Na O
-
O Na
+
+ Cl Cl
-NaCl
CH3
Disodium salt of Bisphenol A Phosgene

O
CH3
O O
CH3 n
Lexan
(a polycarbonate)
Chapter 18

End
Chapter 18