Reactions of

Carboxylic Acids
and Esters
• Apply the basic rules of nomenclature of carboxylic acids and its
derivatives, converting between structures and names and vice versa.
• Relate the structure and physical properties of carboxylic acids and
esters.
• Write a reaction mechanism to illustrate how an ester can be formed
from a carboxylic acid.
• Draw the structures of alcohols produced from the reduction of
carboxylic acids.
• Predict the products of the reaction of carboxylic acid derivatives with
Grignard reactants.
• Compare and contrast the mechanism of ester hydrolysis using acids
and bases.
 NOMENCLATURE OF CARBOXYLIC ACIDS

In IUPAC nomenclature, carboxylic acids are identified by a suffix added to the

parent name of the longest chain, and two different endings are used
depending on whether the carboxy group is bonded to a chain or ring.

• [1] If the COOH is bonded to a chain of carbons, find the longest chain
containing the COOH group, and change the -e ending of the parent alkane
to the suffix -oic acid. If the COOH group is bonded to a ring, name the ring
and add the words carboxylic acid.

• [2] Number the carbon chain or ring to put the COOH group at C1, but omit
this number from the name. Apply all of the other usual rules of
nomenclature.
 SAMPLE PROBLEM

Give the IUPAC name for each compound.

1.

2.
SOLUTION
 SAMPLE PROBLEM

Give the IUPAC name for each compound.

1. 3.

2.
 SAMPLE PROBLEM

Give the structure corresponding to each IUPAC

name.
1. 2-bromobutanoic acid

2. 2,3-dimethylpentanoic acid

3. 3,3,4-trimethylheptanoic acid
 Naming an Acid Chloride—RCOCl

Acid chlorides are named by naming the acyl group and

adding the word chloride. Two different methods are
used.
[1] For acyclic acid chlorides: Change the suffix -ic acid of the parent carboxylic
acid to the suffix -yl chloride; or
[2] When the COCl group is bonded to a ring: Change the suffix -carboxylic acid
to -carbonyl chloride.
 Naming an Anhydride

The word anhydride means “without water.” Removing

one molecule of water from two molecules of carboxylic
acid forms an anhydride.
 Naming an Anhydride

Symmetrical anhydrides are named by changing the acid ending of the parent
carboxylic acid to the word anhydride. Mixed anhydrides, which are derived
from two different carboxylic acids, are named by alphabetizing the names for
both acids and replacing the word acid by the word anhydride.
 Naming an Ester – RCOOR’

An ester has two parts to its structure, each of which must be named: an acyl
group (RCO-) and an alkyl group (designated as R') bonded to an oxygen atom.
In the IUPAC system, esters are identified by the
suffix -ate.
Example Give a systematic name for each ester:

1. 2.
 Naming an Ester – RCOOR’

Step [1] Name the R' group bonded to the oxygen atom as an
alkyl group.
•The name of the alkyl group, ending in the suffix -yl, becomes
the first part of the ester name.
 Naming an Ester – RCOOR’

Step [2] Name the acyl group (RCO) by changing

the -ic acid ending of the parent carboxylic acid to
the suffix -ate.
•The name of the acyl group becomes the second part of
the name.
 Nomenclature—Amides

• All 1° amides are named by replacing the -ic acid, -oic acid, or -
ylic acid ending with the suffix amide.

17
 SAMPLE PROBLEM

Example Give a systematic name for each amide:

1.

2.
 SOLUTION
Step [1]
Name the alkyl group (or groups) bonded to the N atom of the amide. Use the prefix “N-”
preceding the name of each alkyl group.

The names of the alkyl groups form the first part of each amide name.

For 3° amides, use the prefix di- if the two alkyl groups on N are the same. If the two
alkyl groups are different, alphabetize their names. One “N-” is needed for each alkyl
group, even if both R groups are identical.
1. 2.

The compound is a 3° amide with two methyl groups.

The compound is a 2° amide with Use the prefix di- and two “N-” to begin the name → N,N-
one ethyl group → N-ethyl. dimethyl.
 SOLUTION
Step [2] Name the acyl group (RCO) with the suffix -amide.

Change benzoic acid to benzamide.

Put the two parts of the name together.

Answer: N,N-dimethylbenzamide
 Nomenclature—Nitriles

• In contrast to the carboxylic acid derivatives, nitriles are named as

alkane derivatives.
• Find the longest chain that contains the CN and add the word
nitrile to the name of parent alkane.
• Number the chain to put CN at C1, but omit this number from the
name.
• Common names of nitriles are derived from the names of the
carboxylic acid having the same number of carbon atoms by
replacing the –ic acid ending of the carboxylic acid with the suffix
–onitrile.
• When the CN is named as a substituent it is called a cyano group.
21
 Nomenclature—Nitriles

• CH3CH2CH2CN is butanenitrile, not propanenitrile.

Figure 22.1

22
23
 SAMPLE PROBLEM

Give the IUPAC name for each compound.

 SOLUTION
a. The functional group is an acid chloride bonded to a chain of atoms, so the name
ends in -yl chloride.

[1] Find and name the longest chain containing the COCl:

[2] Number and name the substituents:

 SOLUTION

b. The functional group is an ester, so the name ends in -ate.

[1] Find and name the longest chain containing the carbonyl group:

[2] Number and name the substituents:

 SAMPLE PROBLEM

Give an IUPAC or common name for each compound.

1. 3.

2. 4.
 SAMPLE PROBLEM

Give the structure corresponding to each IUPAC

name.
1. 5-methylheptanoyl chloride

2. isopropyl propanoate

3. acetic formic anhydride

4. N-isobutyl-N-methylbutanamide
 CONCEPT CHECK

Give the IUPAC or common name for each compound:

1. 2.

Give the structure corresponding to each IUPAC name.

3. 3-methylpentanenitrile
4. o-cyanobenzoic acid
5. sec-butyl 2-methylhexanoate
6. N-ethylhexanamide
PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS
 RECALL:
Fischer Esterification of Carboxylic Acids
• Treatment of a carboxylic acid with an alcohol in the presence of an acid
catalyst forms an ester.
• This reaction is called a Fischer esterification.
• The reaction is an equilibrium, so it is driven to the right by using excess
alcohol or by removing water as it is formed.

32
33
 Preview of Oxidation and Reduction

• Carbonyl compounds can be either reactants or products in

oxidation–reduction reactions.

34
 Oxidation and Reduction of Carbonyl Compounds
• The three most useful oxidation and reduction reactions of
carbonyl starting materials can be summarized as follows:

35
 LiAlH4 Reductions

• Carboxylic acids are reduced to 1° alcohols with LiAlH4.

• LiAlH4 is too strong of a reducing agent to stop the reaction at the
aldehyde stage, but milder reagents are not strong enough to
initiate the reaction in the first place.

36
37
 Reactivity of Common Organometallic Compounds

• Since both Li and Mg are very electropositive metals, organolithium (RLi)

and organomagnesium (RMgX) reagents contain very polar carbon-metal
bonds and are therefore very reactive reagents.
• Organomagnesium reagents are called Grignard reagents.
• Organocopper reagents (R2CuLi), also called organocuprates, have a
less polar carbon–metal bond and are therefore less reactive.
• Although they contain two R groups bonded to Cu, only one R group is
utilized in the reaction.
• In organometallic reagents, carbon bears a − charge.

38
 Preparation of Organolithium Compounds

• Organolithium and Grignard reagents are typically prepared by

reaction of an alkyl halide with the corresponding metal.

• With lithium, the halogen and metal exchange to form the

organolithium reagent.
• With Mg, the metal inserts in the carbon–halogen bond, forming the
Grignard reagent.
39
 Solvent Stabilization of Grignard Reagents

• Grignard reagents are usually prepared in diethyl ether

(CH3CH2OCH2CH3) as solvent.
• It is thought that two ether O atoms complex with the Mg atom,
stabilizing the reagent by Lewis Base–Lewis Acid interactions.

40
 Organometallic Reactions with Esters and Acid Chlorides

• Organometallic reagents react with carboxylic acid derivatives

(RCOZ) to form two different products, depending on identity of
both the leaving group (Z) and the reagent R-M.
• The most useful reactions are carried out with esters and acid
chlorides, forming either ketones or 3° alcohols.

41
 Organometallic Reactions with Esters and Acid Chlorides

• Both esters and acid chlorides form 3° alcohols when treated with
two equivalents of either Grignard or organolithium reagents.

42
43
 Grignard Reaction with CO2

• Grignards react with CO2 to give carboxylic acids after protonation with aqueous acid.
• This reaction is called carboxylation.
• The carboxylic acid formed has one more carbon atom than the Grignard reagent from which
it was prepared.

44
 Sample Problem

Draw the product formed when each compound is

treated with two equivalents of CH3CH2CH2CH2MgBr
followed by H2O.
1.

2.

3.
 Sample Problem

What ester and Grignard reagent are needed to prepare

the following alcohol?
 SOLUTION

A 3° alcohol formed from an ester and Grignard reagent

must have two identical R groups, and these R groups
come from RMgX. The remainder of the molecule comes
from the ester. The carbon (labeled in blue) bonded to
the OH group comes from the carbonyl carbon.
 SOLUTION

Checking in the synthetic direction:

 Sample Problem

What ester and Grignard reagent are needed to prepare

each alcohol?
1.

2.

3.
 Reactions of Esters

• Esters are hydrolyzed with water in the presence of either acid or base to
form carboxylic acids or carboxylate anions, respectively.

• Esters react with NH3 and amines to form 1°, 2°, or 3° amides.

50
51
 Base Hydrolysis of Esters

• Basic hydrolysis of an ester is also called saponification.

• Hydrolysis is base promoted, not base catalyzed, because the

base (OH–) is the nucleophile that adds to the ester and forms part
of the product.
• It participates in the reaction and is not regenerated later.

52
 Base Hydrolysis of Esters

• Hydrolysis is base promoted, not base catalyzed, because the

base (OH–) is the nucleophile that adds to the ester and forms part
of the product.
• It participates in the reaction and is not regenerated later.

53
 Basic Hydrolysis of Esters

• The carboxylate anion is resonance stabilized, and this drives the

equilibrium in its favor.
• Once the reaction is complete and the anion is formed, it can be
protonated with strong acid to form the neutral carboxylic acid.

54
 Sample Problem

Fenofibrate is a cholesterol-lowering medication that is

converted to fenofibric acid, the active drug, by
hydrolysis during metabolism. What is the structure of
fenofibric acid?