Chem 104

Organic Acids and their

Derivatives
By
Fraulein C. Cabanag
Carboxylic Acids
› characterized by the carboxyl group, shown in red, which
may also be written in condensed form as —COOH or —
CO2H.
› Carboxylic is taken from carbonyl and hydroxyl, the two
structural units that make up the carboxyl group.
› Acid in the name tells us one of the more important
properties of these molecules:
› Partially dissociate in water to release protons, thus they
are weak acids.
Carboxylic Acids
Structure and Physical Properties
› The carboxyl group consists of two very polar functional
groups, the carbonyl group and the hydroxyl group;
carboxylic acids are very polar compounds.
› they can hydrogen bond to one another and to molecules
of a polar solvent such as water.
› Due to intermolecular hydrogen bonding, they boil at
higher temperatures than RCOH, RCOR or ROH of
comparable molecular weight.
Structure and Physical Properties
Structure and Physical Properties
› the smaller carboxylic acids are soluble in water; solubility
falls off dramatically as the carbon content of the carboxylic
acid increases because the molecules become more
hydrocarbon-like and less polar.
› For example, acetic acid (the carboxylic acid found in
vinegar) is completely soluble in water, but hexadecanoic
acid (a sixteen-carbon carboxylic acid found in palm oil) is
insoluble in water
› longer-chain carboxylic acids are generally called fatty
acids and are important components of biological
membranes and triglycerides, the major lipid storage form
in the body
Structure and Physical Properties
Structure and Physical Properties
› lower-molecular-weight carboxylic acids have sharp, sour tastes
and unpleasant aromas.
Examples
› Formic acid, HCOOH, is used as a chemical defense by ants
and causes the burning sensation of the ant bite.
› Acetic acid, CH3COOH, is found in vinegar;
› propionic acid, CH3CH2COOH, is responsible for the tangy
flavor of Swiss cheese
› butyric acid, CH3CH2CH2COOH, causes the stench associated
with rancid butter and gas gangrene.
Structure and Physical Properties
› longer-chain carboxylic acids are generally called fatty
acids and are important components of biological
membranes and triglycerides, the major lipid storage form
in the body
› The functional group is largely responsible for the physical
and chemical properties of the various chemical families.
Exercise
› Which member of each of the following pairs has the lower
boiling point?
a. Hexanoic acid or 3-hexanone
b. 3-Hexanone or 3-hexanol
c. 3-Hexanol or hexane
d. Dipropyl ether or hexanal
e. Hexanal or hexanoic acid
Nomenclature
› Determine the parent compound, the longest continuous
carbon chain bearing the carboxyl group.
› Replace the -e ending of the parent alkane with the suffix -
oic acid. If there are two carboxyl groups, the suffix -dioic
acid is used.
› Number the chain so that the carboxyl carbon is carbon-1.
› Name and number substituents in the usual way.
Nomenclature
Nomenclature
NOMENCLATURE
Nomenclature - Carboxylic acid derivatives of
Cycloalkanes
› named by adding the suffix carboxylic acid to the name of
the cycloalkane or substituted cycloalkane.
› The carboxyl group is always on carbon-1 and other
substituents are named and numbered as usual.
Exercise
› Determine the IUPAC name of each of the ff. structures:
Nomenclature
› Common names end in -ic acid rather than -oic acid.
› substituted carboxylic acids are named as derivatives of
the parent compound
› Greek letters are used to indicate the position of the
substituent.
› The carbon atom bonded to the carboxyl group is the α-
carbon, the next is the β-carbon, and so on.
Nomenclature
Nomenclature – Aromatic carboxylic acids
› In many cases the aromatic carboxylic acids are named, in
either system, as derivatives of benzoic acid.
› Generally, the -oic acid or -ic acid suffix is attached to the
appropriate prefix.
› However, “common names” of substituted benzoic acids
(for example, toluic acid and phthalic acid) are frequently
used.
Nomenclature – Aromatic carboxylic acids
Nomenclature – Aromatic carboxylic acids
› Often the phenyl group is
treated as a substituent,
and the name is derived
from the appropriate
alkanoic acid parent chain.
Exercise
› Name the following aromatic carboxylic acids:
Exercise
Draw structures for each of the following compounds.
a. o-Toluic acid
b. 2,4,6-Tribromobenzoic acid
c. 2,2,2-Triphenylethanoic acid
Answers
Some important Carboxylic Acids
Many carboxylic acids occur in nature.
› Fatty acids can be isolated from a variety of sources including
palm oil, coconut oil, butter, milk, lard, and tallow (beef fat).
More complex carboxylic acids are also found in a variety of
foodstuffs.
> citric acid is found in citrus fruits and is often used to give the
sharp taste to sour candies. It is also added to foods as a
preservative and antioxidant.
Adipic acid (hexanedioic acid) gives tartness to soft drinks and
helps to retard spoilage.
Some important Carboxylic Acids
› Bacteria in milk produce lactic acid as a product of
fermentation of sugars.
› Lactic acid contributes a tangy flavor to yogurt and
buttermilk.
› It is also used as a food preservative to lower the pH to a
level that retards microbial growth that causes food
spoilage. Lactic acid is also produced in muscle cells when
an individual is exercising strenuously.
› If the level of lactic acid in the muscle and bloodstream
becomes high enough, the muscle can’t continue to work.
Some important Carboxylic Acids
Reactions involving Carboxylic Acids
Preparation of Carboxylic Acids
› Many of the small carboxylic acids are prepared on a
commercial scale.
› A variety of oxidizing agents, including oxygen, can be
used, and catalysts are often required to provide
acceptable yields.
› Other simple carboxylic acids can be
made by oxidation of the appropriate primary alcohol or
aldehyde.
Preparation of Carboxylic Acids
Preparation of Carboxylic Acids
› In the laboratory, carboxylic acids are prepared by the
oxidation of aldehydes or primary alcohols. Most common
oxidizing agents, such as chromic acid, can be used
Reactions involving Carboxylic Acids
Acid-Base Reactions
› The carboxylic acids behave as acids because they are
proton donors.
› They are weak acids that dissociate to form a carboxylate
ion and a hydrogen ion
Acid-Base Reactions
› Carboxylic acids are weak acids because they dissociate
only slightly in solution.
› Typically, less than 5% of the acid is ionized (approximately
five carboxylate ions to every ninety-five carboxylic acid
molecules)
› When strong bases are added to a carboxylic acid,
neutralization occurs.
›
Acid-Base Reactions
› The acid protons are removed by the OH- to form water
and the carboxylate ion. The equilibrium shown in the
reaction is shifted to the right, owing to removal of H+.
Acid-Base Reactions - Examples
Example 1
Answer
Example 2
Salts of Carboxylic Acids
› are ionic substances.
› As a result, they are very soluble in water.
› The long-chain carboxylic acid salts (fatty acid salts) are
called soaps
Exercise
Answers
Esters
› Esters are carboxylic acid derivatives, organic
compounds derived from carboxylic acids.
› They are formed from the reaction of a carboxylic acid with
an alcohol, and both of these reactants are reflected in the
naming of the ester.
Esters
Structure and Physical Properties
• are mildly polar and have pleasant aromas.
• Many esters are found in natural foodstuffs;
banana oil (3-methylbutyl ethanoate; common name, isoamyl
acetate),
pineapples (ethyl butanoate; common name, ethyl butyrate)
• raspberries (isobutyl methanoate; common name, isobutyl
formate)
• Esters boil at approximately the same temperature as
aldehydes or ketones of comparable molecular weight.
• The simpler ones are somewhat soluble in water.
 Flavor and Fragrance

• It is the smell you perceive in rancid butter. Butyric acid is also

a product of fermentation reactions carried out by Clostridium
perfringens. This organism is the most common cause of gas
gangrene. Butyric acid contributes to the notable foul smell
accompanying this infection.
Flavor and Fragrance
Flavor and Fragrance
Flavor and Fragrance
Flavor and Fragrance
Nomenclature
› Use the alkyl or aryl portion of the alcohol name as the first
name.
› The -ic acid ending of the name of the carboxylic acid is
replaced with –ate and follows the first name.
› Example
Example 1
Example 2
Nomenclature
› Naming esters is analogous to naming the salts of carboxylic
acids.
› Consider the following comparison:

› the alkyl group of the alcohol, rather than Na, has displaced the
acidic hydrogen of the carboxylic acid.
Reactions Involving esters
Preparation of esters
› The conversion of a carboxylic acid to an ester requires
heat and is catalyzed by a trace of acid (H+).
› When esters are prepared directly from a carboxylic acid
and an alcohol, a water molecule is lost
Example
Exercise
Hydrolysis of Esters
› Esters undergo hydrolysis reactions in water
› This reaction requires heat. A small amount of acid (H) may
be added to catalyze the reaction
Hydrolysis of Esters Example
Hydrolysis of Esters
› Under basic conditions the salt of the carboxylic acid is
actually produced.
Hydrolysis of Esters
› The carboxylic acid is formed when the reaction mixture is
neutralized with an acid such as HCl.
Exercise
Answers
Hydrolysis of Esters
› Fats and oils are triesters of the alcohol glycerol.
› When they are hydrolyzed by saponification, the products are soaps,
which are the salts of long-chain carboxylic acids (fatty acid salts).
The carbon content of the fatty acid salts governs the solubility of a
soap.
› The lower-MW carboxylic acid salts (up to twelve carbons) have
greater solubility in water and give a lather containing large bubbles.
› The higher-MW carboxylic acid salts (fourteen to twenty carbons) are
much less soluble in water and produce a lather with fine bubbles.
› The nature of the cation also affects the solubility of the soap.
› In general, the potassium salts of carboxylic acids are more soluble
in water than the sodium salts
Soap
› The role of soap in the removal of soil and grease is best
understood by considering the functional groups in soap
molecules and studying the way in which they interact with oil
and water.
› The long, continuous hydrocarbon side chains of soap
molecules resemble alkanes, and they dissolve other nonpolar
compounds such as oils and greases (“like dissolves like”).
› The large nonpolar hydrocarbon part of the molecule is
described as hydrophobic, which means “water-fearing.”
› This part of the molecule is repelled by water. The highly polar
carboxylate end of the molecule is called hydrophilic, which
means “water-loving.”
Saponification – base catalyzed hydrolysis of a
glycerol triester
› When soap is dissolved in
water, the carboxylate end
actually dissolves.
› The hydrocarbon (HC) part
is repelled by the water
molecules so that a thin
film of soap is formed on
the surface of the water
with the HC chains
protruding outward.
› When soap solution comes
in contact with oil or
grease, the HC part
dissolves in the oil or
grease, but the polar COO-
group remains dissolved in
water.
› When particles of oil or
grease are surrounded by
soap molecules, the
resulting “units” formed are
called micelles
› Micelles repel one another as
they are surrounded on the
surface by the negatively
charged carboxylate ions.
› Mechanical action, e.g.,
scrubbing or tumbling in a
washing machine, causes oil
or grease to be surrounded
by soap molecules and
broken into small droplets so
that relatively small micelles
are formed.
Polymers
› polymers are macromolecules, very large molecules.
› They result from the combination of many smaller
molecules, usually in a repeating pattern, to give molecules
whose molecular weight may be 10,000 g/mol or greater.
› The small molecules that make up the polymer are called
monomers.
› A polymer may be made from a single type of monomer.
Such a polymer would have the following general structure:
~A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A~
Condensation Polymers
› Alternatively, two different monomers may be
copolymerized, producing a polymer with the following
structure:
~A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B~
› E.g. of this type are polyesters; known as condensation
polymers
› Condensation polymers are formed by the polymerization
of monomers in a reaction that forms a small molecule
such as water or an alcohol. Polyesters are synthesized by
reacting a dicarboxylic acid and a dialcohol (diol).
CONDENSATION
POLYMERS
PETE
› can be used to make shatterproof plastic bottles, e.g.,
those used for soft drinks.
› However, these bottles cannot be recycled and reused
directly because they cannot withstand the high
temperatures required to sterilize them.
› can’t be used for any foods, such as jellies, that must be
packaged at high temperatures. A new plastic, PEN, or
polyethylene naphthalate, is used.
Polyesters
› When formed as fibers, polyesters are used to make fabric for
clothing.
› Trendy in the 1970s, during the “disco” period
› Polyester fabrics, and a number of other synthetic polymers
used in clothing, have become even more fashionable since the
introduction of microfiber technology.
› Synthetic polymers are extruded into fibers that are only half
the diameter of fine silk fibers.
› The result is a fabric that drapes freely yet retains its shape.
These fabrics are generally lightweight, wrinkle resistant, and
remarkably strong.
Acid Chlorides and Acid Anhydrides
Acid Chlorides
› are carboxylic acid derivatives having the general formula

› They are named by replacing the -ic acid ending of the

common name with -yl chloride or the -oic acid ending of the
I.U.P.A.C. name of the carboxylic acid with -oyl chloride.
Acid Chlorides
Acid Chlorides
› Noxious, irritating chemicals and must be handled with
great care.
› Slightly polar and boil at approximately the same
temperature as the corresponding aldehyde or ketone of
comparable molecular weight.
› React violently with water and therefore cannot be
dissolved in that solvent.
› Have little commercial value other than their utility in the
synthesis of esters and amides, two of the other carboxylic
acid derivatives.
Preparation of Acid Chlorides
› Prepared from the corresponding carboxylic acid by
reaction with one of several inorganic acid chlorides,
including PCl3, PCl5, or SOCl2.
Preparation of Acid Chlorides - Examples
Naming Acid Chlorides
Hydrolysis of Acid Chlorides
› React violently with water
› The products are the carboxylic acid and hydrochloric acid.
Exercise
ANSWERS
Acid Anhydrides
› are molecules with the following general formula

› The structure above reveals that acid anhydrides are

actually two carboxylic acid molecules with a water
molecule removed.
› The word anhydride means “without water.”
Acid Anhydrides
Acid Anhydrides
› Acid anhydrides are classified as symmetrical if both acyl
groups are the same.
› Symmetrical acid anhydrides are named by replacing the
acid ending of the carboxylic acid with the word
anhydride.
Unsymmetrical Acid Anhydrides
› those having two different acyl groups.
› named by arranging the names of the two parent
carboxylic acids and following them with the word
anhydride.
› The names of the carboxylic acids may be arranged
by size or alphabetically.
Preparation of Acid Anhydrides
› Most acid anhydrides cannot be formed in a reaction
between the parent carboxylic acids.
› One typical pathway for the synthesis of an acid anhydride
is the reaction between an acid chloride and a carboxylate
anion.
Preparation of Acid Anhydrides
› The synthesis of ethanoic anhydride from ethanoic acid
Hydrolysis of Acid Anhydrides
› Acid anhydrides readily undergo hydrolysis.
› The rate of the hydrolysis reaction may be increased by the
addition of a trace of acid or hydroxide base to the
solution.
Example
NOMENCLATURE
Exercise
ANSWERS
Acyl group transfer
› Acid anhydrides can also react with an alcohol.
› This reaction produces an ester and a carboxylic acid.
› This is an example of an acyl group transfer reaction
Other Acyl group donors
› Include thioesters and esters.
› Acyl transfer reactions are very important in nature,
particularly in the pathways responsible for breakdown of
food molecules and harvesting cellular energy.
Nature’s high energy compounds:
Phosphoesters and Thioesters
1. Phospohoesters
› An alcohol can react with phosphoric acid to produce a
phosphate ester, or phosphoester

› are simple sugars or monosaccharides; very important in the

energy-harvesting biochemical pathways that provide energy
for all life functions.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› One such pathway is glycolysis; comes from two Greek
words that mean “splitting sugars” (glykos, “sweet,” and
lysis, “to
split”).
› In this pathway, the six-carbon sugar glucose is split, and
then oxidized, to produce two three-carbon molecules,
called pyruvate.
› This pathway is the first stage in the breakdown of
sugars. The first reaction in this pathway is the formation of
a phosphate ester of the six-carbon sugar, glucose.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› The phosphorylation of glucose to produce glucose-
6-phosphate
Nature’s high energy compounds:
Phosphoesters and Thioesters
› In the phosphorylation of glucose, the source of the phosphoryl
group is adenosine triphosphate (ATP), which is the universal
energy currency for all living organisms.
› ATP is used to store energy released in cellular metabolic
reactions and provides the energy required for most of the
reactions that occur in the cell.
› The transfer of a phosphoryl group from ATP to glucose
“energizes” the glucose molecule in preparation for other
reactions of the pathway.
› Phosphoryl – used to describe the functional group derived
from phosphoric acid that is part of another molecule.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› ATP consists of a nitrogenous base (adenine) and a
phosphate ester of the five-carbon sugar ribose.
› The triphosphate group attached to ribose is made up of
three phosphate groups bonded to one another by
phosphoric anhydride bonds.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› When two phosphate groups react with one another, a
water molecule is lost.
NATURE’S HIGH ENERGY
COMPOUNDS:
PHOSPHOESTERS AND
THIOESTERS
The hydrolysis of the
phosphoric anhydride bond
of ATP is accompanied
by the release of energy
that is used for biochemical
reactions in the cell.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› The energy of ATP is made available through hydrolysis of
either of the two phosphoric anhydride bonds.
› an exothermic process; that is, energy is given off.
› When the phosphoryl group is transferred to another
molecule—for instance, glucose—some of that energy
resides in the phosphorylated sugar, thereby “energizing”
it.
› The importance of ATP as an energy source becomes
apparent when we synthesize and break down an
amount of ATP equivalent to our body weight each day.
Nature’s high energy compounds:
Phosphoesters and Thioesters
2. Thioesters
› Cellular enzymes can carry out a reaction between a thiol and a
carboxylic acid to produce a thioester:

› The reactions that produce thioesters are essential in energy-

harvesting pathways as a means of “activating” acyl groups for
subsequent breakdown reactions.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› The complex thiol coenzyme A is the most important acyl
group activator in the cell.
› The detailed structure of coenzyme A is generally
abbreviated CoA—SH to emphasize the importance of the
sulfhydryl group.
› The most common thioester is the acetyl ester, called
acetyl coenzyme A (acetyl CoA).
Nature’s high energy compounds:
Phosphoesters and Thioesters
› Acetyl CoA carries the acetyl group from glycolysis or β-
oxidation of a fatty acid to an intermediate of the citric acid
cycle.
› This reaction is an example of an acyl group transfer
reaction where the acyl group donor is a thioester—
acetyl CoA.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› The acyl group being transferred is the acetyl group, which
is transferred to the carbonyl carbon of oxaloacetate.
Nature’s high energy compounds:
Phosphoesters and Thioesters
› the citric acid cycle is an energy-harvesting pathway that
completely oxidizes the acetyl group to two CO2 molecules.
› The electrons that are harvested in the process are used to
produce large amounts of ATP.
› Coenzyme A also serves to activate the acyl group of fatty
acids during β-oxidation, the pathway by which fatty acids
are oxidized to produce ATP.