Chapter 16

Carboxylic Acids,
Esters, and Other
Acid Derivatives
 Section 16.1
Structure of Carboxylic Acids and Their Derivatives

• Carboxylic acid: An organic compound with carboxyl

functional group
• Carboxyl group: A carbonyl group (C=O) with a hydroxyl
group (—OH) bonded to the carbonyl carbon atom
• A general structural representation for a carboxyl group
is shown below Carbonyl group

R C OH
Carboxylic acid
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 Section 16.1
Structure of Carboxylic Acids and Their Derivatives

• Carboxylic acid derivative: An organic compound

synthesized from or converted into a carboxylic acid.
• Four important carboxylic acid derivatives:
– Esters
– Acid chlorides
– Acid anhydrides
– Amides

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 Section 16.2
IUPAC Nomenclature for Carboxylic Acids

IUPAC Rules for Naming Monocarboxylic Acids

• Rule 1: Select the longest carbon chain that includes the
carbon atom of the carboxyl group as the parent chain.
• Rule 2: Name the parent chain by changing the “-e”
ending of the corresponding alkane to “-oic” acid.
• Rule 3: Number the parent chain by assigning the #1 to
the carboxyl carbon atom. Name: alkanoic acid
• Rule 4: Determine the identity and location of any
substituents in the usual manner, and append this
information to the front of the parent chain name.

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 Section 16.2
IUPAC Nomenclature for Carboxylic Acids

Dicarboxylic and Saturated Acids

• Dicarboxylic Acids: Carboxylic acid that contains two
carboxyl groups.
• Saturated acids: Named by appending the suffix “-dioic”
acid to the corresponding alkane name.
• IUPAC name: alkanedioic acid

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 Section 16.2
IUPAC Nomenclature for Carboxylic Acids

Aromatic Carboxylic Acids

• The simplest aromatic carboxylic acid is called benzoic
acid.
• Other simple aromatic acids are named as derivatives of
benzoic acid.

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 Section 16.3
Common Names for Carboxylic Acids

• Common names are usually derived from some Latin or

Greek word that is related to a source for the acid.
• Name of a monocarboxylic acid is formed by taking the
Latin or Greek root name for the specific number of
carbon atoms and appending the suffix “–ic” acid.
− The positions of substituents are denoted by Greek
alphabet rather than numbers with reference to the
carbonyl carbon (C1), e.g., C2 is alpha (), C3 is beta
(), C4 is gamma (), and C5 is delta ().

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 Section 16.3
Common Names for Carboxylic Acids

First Six Unbranched Monocarboxylic Acids

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 Section 16.3
Common Names for Carboxylic Acids

First Six Unbranched Dicarboxylic Acids

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 Section 16.3
Common Names for Carboxylic Acids

Common Acids
• Acetic Acid: CH3COOH
– Vinegar is 4%-8% (v/v) acetic acid solution
– Colorless liquid with sharp odor
• Oxalic acid: HOOC-COOH - found in spinach and
cabbage
– Harmful at high concentrations
– Used to remove rust, bleach straw, and leather and
ink stains

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 Section 16.4
Polyfunctional Carboxylic Acids

• PCAs contain at least one or more functional groups

other than carboxyl group
• PCAs are commonly found in living organisms and play
an important role in human body
– Occur in many fruits
– Used in over the counter skin care products and
prescription drugs
• Common types of PCAs:
– Unsaturated acids
– Hydroxy acids
– Keto acids

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 Section 16.4
Polyfunctional Carboxylic Acids

Unsaturated Acids
• Contain at least one carbon-carbon double bond (C=C):
• Two types of monounsaturated carboxylic acids:
– Trans - unsaturated carboxylic acids
– Cis – unsaturated carboxylic acids
• Examples:
– Propenoic acid (acrylic acid) used in the manufacture
of polymeric materials.
– Futenedioic acid - has two forms
• Fumaric acid : trans-form
• Maleic acid: cis-form

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 Section 16.4
Polyfunctional Carboxylic Acids

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 Section 16.4
Polyfunctional Carboxylic Acids

Hydroxy Acids
• Contain at least one hydroxyl group and are naturally present in
many foods
• Examples:
– Glycolic acid: present in juice from sugar cane and sugar beets
– Lactic acid: Present sour milk, sauerkraut, and dill pickles
– Malic acid and tartaric acid occur naturally in fruits

Malic acid

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 Section 16.4
Polyfunctional Carboxylic Acids

Keto Acids
• Contain a carbonyl (C=O) group within a carbon chain.
• Example:
– Pyruvic acid - simplest keto acid with odor resembling
that of vinegar (acetic acid) and it is also a metabolic
acid

Oxaloacetic acid

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 Section 16.5
Metabolic Carboxylic Acids

• Metabolic acids: Polyfunctional acids formed as

intermediates of metabolic reactions in the human body.
• There are eight such acids that will appear repeatedly in
biochemistry.
• Metabolic acids are derived from:
− Propionic acid, (C3 mono acids): lactic, glyceric, and
pyruvic acids
− Succinic acid (C4 diacid): fumaric, oxaloacetic, and
malic acids
− Glutaric acid (C5 diacid): -ketoglutaric and citric
acids (C6 tricarboxylic acid)

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 Section 16.6
Physical Properties of Carboxylic Acids

At Room Temperature and Pressure

• Straight chain carboxylic acids with 1-9 carbon atoms
are liquids and have strong odors
• Straight chain carboxylic acids with >10 C atoms are
waxy solids with no odor.
• Aromatic and dicarboxylic acids: Odorless solids

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 Section 16.6
Physical Properties of Carboxylic Acids

Melting and Boiling Points

• Most are polar organic compounds because of the
presence of polar C=O and polar -OH groups
• Form H-bonding due to strong polar groups
• Therefore have highest melting and boiling points
compared to those of other types of compounds.

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 Section 16.6
Physical Properties of Carboxylic Acids

• A given carboxylic acid molecule form two hydrogen

bonds to another carboxylic acid molecule, producing a
“dimer”, a complex with a mass twice that of a single
molecule.

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 Section 16.7
Preparation of Carboxylic Acids

• Non-aromatic carboxylic acids: Oxidation of primary alcohols or

aldehydes, using an oxidizing agent such as K2Cr2O7
• Aromatic carboxylic acids: Oxidation of a carbon side chain
(alkyl group) on a benzene derivative
• Examples:
O
[O] [O]
HO HO
O
Ethanol Acetaldehyde Acetic acid

CH2CH2CH3 COOH
K2Cr2O 7
+ CO2 + 3H 2O
H2SO 4
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 Section 16.8
Acidity of Carboxylic Acids

• Carboxylic acids are weak acids

• In water they dissociate to release protons (H+) and form
carboxylate ion (RCOO-) -- equilibrium reactions and
equilibrium lies towards the left indicating that small
amount of acid is ionized
• Monocarboxylic acids release one H+ to form carboxylate
ion with one negative charge
• Dicarboxylic acids release two H+ ions to form
carboxylate ion with two negative charges and so on

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 Section 16.9
Carboxylic Acid Salts

• Carboxylic acids react with bases to form salt and water

– R-COOH + NaOH  R-COONa + H2O
• Naming carboxylic acid salts :
– Positive ion name (Na+, K+ etc) followed by anion (RCOO-) name
(drop “-ic acid” and replace with “-ate”)
– Names of anion and cation are written as separate words
– Example 1: CH3COO-Na+ -- Sodium acetate
– Example 2: C6H5COO-K+ -- Potassium benzoate
• Carboxylic acid salts are more soluble in water than their parent
acids due to ion-dipole interaction.
– Example: Benzoic acid = 3.4 g/L; sodium benzoate = 550g/L

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 Section 16.9
Carboxylic Acid Salts

Uses of Carboxylic Acid Salts

• Good antimicrobial and antifungal agents
• Benzoate salts: Effective (0.1%, m/m) against yeast and
mold in beverages, jams and jellies, etc.
• Sodium sorbate: Inhibits mold and yeast in dairy
products, dried fruits, some meat and fish products
• Propionate: Used in preservation of baked goods
• Benzoate and sorbate can’t be used in yeast leavened
baked goods as they inhibit mold and yeast

Sorbic acid
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 Section 16.10
Structure of Esters

• An ester is a carboxylic acid derivative in which the —

OH portion of the carboxyl group has been replaced with
an —OR group
• The simplest ester, which has two carbon atoms, has a
hydrogen atom attached to the ester functional group
HCOOCH3
• There are two three-carbon esters
• The simplest aromatic ester is derived from benzoic acid

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 Section 16.11
Preparation of Esters
• Esters are produced by an esterification reaction
• Esterification reaction: Reaction of a carboxylic acid with
an alcohol (or phenol) to produce an ester
• Esterification reaction require a strong acid catalyst such
as H2SO4

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 Section 16.12
Nomenclature of Esters
• The name for the alcohol part of the ester appears first and is
followed by a separate word giving the name for the acid part of
the ester.
• The name for the alcohol part of the ester is simply the name of the
R group (alkyl, cycloalkyl, or aryl) present in the —OR portion of the
ester.
• The name for the acid part of the ester is obtained by dropping the
“-ic” acid ending for the acid’s name and adding the suffix “-ate.”

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 Section 16.13
Selected Common Esters

Flavor/Fragrance Agents
• Esters are largely responsible for the flavor and
fragrance of fruits and flower
• Generally the natural flavor or odor is due to a mixture of
esters with one dominant ester
• The structures of esters in natural flavors are closely
related to one another
• Example, the apple and pineapple flavoring agents differ
by one carbon atom (methyl versus ethyl)

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 Section 16.14
Isomerism for Carboxylic Acids and Esters
• Functional Group Isomers: Carboxylic acids and esters
with the same number of carbon atoms and the same
degree of saturation
• Skeletal Isomers: Both carboxylic acid and esters exhibit
skeletal isomers
• Positional Isomers: Esters exhibit positional isomerism,
i.e., the functional group can change its position

• CH3CH2COOCH3 CH3CH2CH2COOH functional isomers

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Section 16.14
Isomerism for Carboxylic Acids and Esters

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 Section 16.15
Physical Properties of Esters

• No hydrogen atom attached to oxygen atoms, therefore

they don’t form H-bonding among other molecules of
itself
• Therefore have lower BP than those of alcohols and
acids
• Lower molecular weight esters are soluble in water
because they can from H-bonding with water molecules
• Esters with 5 or more carbon atoms are sparingly
soluble in water
• Esters have pleasant odor

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 Section 16.15
Physical Properties of Esters

• Low-molecular-mass esters are soluble in water because

of ester–water hydrogen bonding.

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 Section 16.19
Acid Chlorides and Acid Anhydrides
• Acid Anhydrides: A carboxylic acid derivative in which the “-OH”
portion of the carboxyl group has been replaced with a “acyl”
group.
• Two types of acid anhydrides:
− Symmetrical acid anhydrides
− Mixed anhydrides
• General reaction

O O O O

R C OH + HO C R' R C O C R' + H2O

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 Section 16.19
Acid Chlorides and Acid Anhydrides

• Acid Chloride: A carboxylic acid derivative in which the “-

OH” portion of the carboxyl group has been replaced
with a “-Cl” atom.
• Naming Acid Chlorides
– Replace the “-ic acid” ending of the common name of
the parent carboxylic acid with “–yl chloride.”
– Replace the “-oic acid” ending of the IUPAC name of
the parent carboxylic acid with “-oyl chloride.”

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 Section 16.19
Acid Chlorides and Acid Anhydrides

CN = acetyl chloride

IUPAC Name = ethanoyl chloride

Benzoyl chloride
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 Section 16.1
Structure of Carboxylic Acids and Their Derivatives

N,N-dimethyl formamide Acetamide Benzamide

N,N-dimethyl methanamide ethanamide

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 Section 16.1
Structure of Carboxylic Acids and Their Derivatives

Amides are formed when the – the –OH of carboxylic acids is

replaced by an amino group

Common name: is derived from the common name of acid

with ending ic acid changed to an amide.
HCONH2 formamide, CH3CONH2 acetamide, CH3CH2CONH2
propionamide

IUPAC name: derived from the alkane with the same

number of carbon, the ending e of alkane changed to amide.
Ex alkanamide

HCONH2 methanamide, CH3CONH2 ethanamide,

CH3CH2CONH2 propanamide Return to TOC

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 Section 16.1
Structure of Carboxylic Acids and Their Derivatives
ANHYDRIDES

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