Carboxylic acids, esters,

and other acid derivatives

Chapter 16

Structure of carboxylic acids

and their derivatives
The functional group present in a carboxylic acid
is a combination of a carbonyl group and a
hydroxyl group; however, the resulting carboxyl
group ( -COOH) possesses properties that are
unlike those present in aldehydes/ketones and
alcohols.

Structure of carboxylic acids

and their derivatives
Carboxylic acids have the following general formula:

Some simple carboxylic acids:

Since carbon can have only four bonds, there are no

cyclic carboxylic acids (i.e. the carboxyl group cannot
form part of a carbon ring)

Structure of carboxylic acids

and their derivatives
The following molecules have a
similar structure to carboxylic acids,
and will be encountered in this
chapter and the next.

IUPAC nomenclature for

carboxylic acids

For monocarboxylic acids (one COOH group):

Select the longest, continuous carbon chain that
involves the carboxyl group. This is the parent
chain and the COOH carbon is designated as C-1.
Name the parent chain by dropping the e from
the corresponding alkane name and changing to
oic acid
Indicate the identity and location of substituents
on acid
Benzoic
the parent chain at the front of the carboxylic acids
name

IUPAC nomenclature for

carboxylic acids
Dicarboxylic acids:
For these compounds, both ends of a chain will
end with a COOH group. The parent chain is
the one that involves both COOH groups.
The parent chain is named as an alkane and
the term dioic acid is added afterwards to
indicate the diacid structure.

Common names for carboxylic

acids

Common names for

dicarboxylic acids

Common names for carboxylic

acids
For common-name carboxylic acids and diacids,
substituents are often numbered using a Greek
system:

So the following molecule could be called Methylpropionic acid (or, using the IUPAC system,
2-Methylpropanoic acid)

Polyfunctional carboxylic
acids
Carboxylic acids that contain other
functional groups besides the COOH
group are called polyfunctional
carboxylic acids. Some examples are
shown below:

Polyfunctional carboxylic
acidsacids
Unsaturated
Unsaturated acids possess a unit of
unsaturation (double/triple C-C bond)
in the structure. Three of the most
common unsaturated acids are
a metabolic acid
shown:

Polyfunctional carboxylic
acids
Hydroxy
acids
Four of the simplest hydroxy acids:

Polyfunctional carboxylic
acids
Keto acids
For keto acids, a carbonyl group is present as part
of a carbon chain that involves a carboxyl group:

For IUPAC naming of this structure, the O-atom of

the carbonyl group is treated as an oxo
substituent and the molecule is called 2Oxopropanoic
acid
Oxo-group

Metabolic carboxylic acids

Polyfunctional acids
are intermediates in
metabolic reactions
that occur as food is
processed to obtain
energy.
Eight key
intermediates in these
processes are derived
from only three
carboxylic acids
(propanoic, butanoic,
and pentanoic acids,
see below)

Physical properties of
carboxylic acids
Carboxylic acids are the most polar
functional group we have seen so far.
The presence of the carbonyl group
next to the OH causes the O-H bond
to be even more polar.

Physical properties of
carboxylic acids

Because of the very polar COOH group,

carboxylic acids exhibit strong intermolecular
attractions.
As expected, carboxylic acids of a given number
of carbon atoms have higher boiling points than
alcohols.
Carboxylic acids also tend to dimerize, producing
molecules that are twice as heavy which have
enhanced London forces (and thus still higher
boiling points).

Physical properties of
carboxylic acids
In terms of water-solubility,
because of H-bonding,
carboxylic acids dissolve
well in water (up to 4carbon chains).
Beyond 4 carbons, watersolubility drops off rapidly.

Preparation of carboxylic
acids
We saw in Ch-15 that carboxylic acids can be
prepared from aldehydes (which can be prepared
from primary alcohols):

Aromatic carboxylic acids can be made by

oxidizing alkyl-substituted aromatic molecules:

Acidity of carboxylic acids

When carboxylic acids are placed in water, they
undergo de-protonation as discussed in Ch-10:

Remember from
Ch-10:
HA + H2O A- +
H3O+

Acidity of carboxylic acids

Acidity of carboxylic acids

Carboxylic acid salts

When carboxylic acids are reacted
with strong bases, they are
converted to salts as follows:

Carboxylic acid salts

Salts of carboxylic acids are much
more water-soluble than the acids
themselves. Also, they can be
converted back to the acid form by
reacting them with a strong acid:

Uses of carboxylic acid salts

Because of their enhanced solubility in water
compared to the acid form, many drugs and
medicines that possess acid groups are marketed
as carboxylic acid salts (sodium or potassium
salts).

frogurt

Structure of esters
Esters are carboxylic acid derivatives
having an alkoxy group instead of a
hydroxyl group.

Preparation of esters
Esters are prepared by condensation reactions
involving carboxylic acids and alcohols. Such
reactions are called esterification reactions:
Reaction is encouraged by the
presence of excess alcohol
(Le Chateliers Principle)

This an ester consists of an acid portion and an

alcohol portion:

Preparation of esters
Cyclic esters (lactones) are created from hydroxy
acids (bear both a hydroxyl group and a carboxyl
group) in an intramolecular esterification
reaction:

Preparation of esters
Indicate the structures of the carboxylic acid and
alcohol that are needed to make each of the
following
esters:
H+
carboxylic acid + alcohol
H O + ester
2

H2O +

H2O +

H2O +

H2O +

H+

H+

H+

H+

Nomenclature for esters

Thinking of an ester in terms of an alcohol portion and a

carboxylic acid portion is important for naming esters
using the IUPAC system:
1. The name for the alcohol portion comes first: name the
alkyl part of the alcohol (e.g., for the ester shown
below, the first part of the esters name is methyl
(alcohol part comes from methanol). Present the alkyl
name separate from the remainder of the ester name.
2. The carboxylic acid portion is named as if it were
deprotonated, changing the -ic Methyl
acid part
of that
propanoate
name to -ate

This part would be called propanoate

Nomenclature for esters

Some other examples:
Ethyl butanoate

Ethyl 2-methylbutanoate
Ethyl -methylbutyrate

2-Methylpropyl butanoate
Isobutyl butanoate

2-Butyl butanoate
Sec-Butyl butanoate

Selected common esters

Flavor/fragrance agents

Selected common esters

Pheromones:

Medications:

Selected common esters

Synthesis of Aspirin

Synthesis of oil of wintergreen:

Isomerism in carboxylic
acids and esters

Recall that constitutional isomers are molecules that share

the same formula but differ in their atom-to-atom
connectivities.
Three kinds of constitutional isomers (in the order we
encountered them):
positional isomers
skeletal isomers
functional group isomers

Carboxylic acids and esters that have a given number of

carbon atoms form another example of functional group
isomers:

Isomerism in carboxylic
acids and esters
For both carboxylic acids and esters,
skeletal isomers are possible:
(carboxylic acids)

(esters)

Isomerism in carboxylic
acids and esters
Positional isomers are possible for esters, but not
carboxylic acids.

Physical properties of esters

Because they dont possess OH groups, esters
cannot form H-bonds with other ester molecules.
As a result, esters have lower boiling points than
carboxylic acids and alcohols that have
approximately the same molar mass.
Water molecules can H-bond to esters, at the
oxygen atoms. This makes low molecule weight
esters water-soluble.

Chemical reactions of esters

Ester hydrolysis: the hydrolysis of an ester is
accomplished by reacting water with the ester in
the presence of an acid catalyst (this is the
reverse reaction of esterification).

An example:

Chemical reactions of esters

Ester saponification: another hydrolysis reaction,
but this time, under basic conditions. Rather than
a carboxylic acid, the acid salt is produced here.

Example:

Sulfur analogs of esters

In Ch-14 and 15, we saw sulfur analogs of
alcohols, ethers, aldehydes, and ketones. Esters
also have known sulfur analogs, thioesters:

Thioesters are made by condensation reactions

involving carboxylic acids and thiols.

Sulfur analogs of esters

Thioesters, like esters, have relatively low boiling
points (compared to alcohols and carboxylic
acids) and may be found in foods as flavorings.
Methyl thiobutanoate

Acetyl coenzyme A, a thioester, is important in

metabolic cycles that provide our bodies with
energy.

Polyesters
In Ch-13, we saw how unsaturated molecules like
ethylene can undergo addition polymerization.
Condensation polymerization creates polymers
through the loss of water molecules:

Difunctional reactants

A polyester

Polyesters
Polyesters are very important materials for
textiles (clothing, upholstery, etc.) and
plastics.
About 50% of PET production goes towards
textiles and the other 50% towards
plastics/materials for applications:
soda bottles
audio/video tapes
medicinal applications like heart valves and
mesh for arterial replacements

Polyesters

Biodegradable polymers are also made by this route.

Polyesters of lactic acid and glycolic acid are used to make
the lactomer shown below, which undergoes hydrolysis
after a few weeks to produce lactic acid and glycolic acid.
Used as materials for sutures, this polymer enables
dissolvable stiches which produce materials that are
already present in the body.

Lactic acid

Glycolic acid

Acid chlorides and acid

anhydrides
Acid chlorides and anhydrides have structures
that are quite similar to carboxylic acids and
esters.
Both are able to be hydrolized to produce
carbolxylic acids.

Acid chlorides are produced by reaction of a

carboxylic acid with an inorganic chloride (PCl 3,
PCl5, or SOCl2).

Acid chlorides and acid

anhydrides
Acid chlorides are named as follows:
first as a carboxylic acid
Remove the -ic acid and add -oyl chloride

Hydrolysis reaction:

Esterificati
on:

Acid chlorides and acid

anhydrides
Acid anhydrides are made by condensation
reactions between carboxylic acids (or between
acid chlorides and carboxylic acids):

Naming is straightforward: indicate the names of

the acids used to make the anhydride (without
the acid part included)

Acid chlorides and acid

Acyl transfer reactions
anhydrides

Carboxylic acids (esters, acid chlorides) possess an acyl

group (notice how this is different that the carboxyl group of
the acid)
Acyl group

Acyl transfer reactions occur during protein synthesis. The

reaction involves the formation of a new bond between the
acyl group and another molecular fragment.
One example of an acyl transfer occurs during an
esterification:

Esters and anhydrides of inorganic

acids
We have seen inorganic acids like H2SO4, H3PO4,
and HNO3 in the first semester of this course.
These can also react with alcohols to make
inorganic esters:

Esters and anhydrides of inorganic

acids
Phosphate esters are the most important class of
inorganic esters.
Because phosphoric acid has three OH groups, it
can form mono-, di- and tri-esters:

Esters and anhydrides of inorganic

acids
Phosphoric acid anhydrides are also made via
condensation reactions:

These systems are important components of cellular

processes for biochemical energy production.