MODULE 6 ALDEHYDES, KETONES, AND CARBOXYLIC ACIDS

INTRODUCTION
The oxidation of primary and secondary alcohols gives different types of products.
Tertiary alcohols are resistant to the usual oxidizing conditions in organic reactions. If we
consider oxidation as the removal of hydrogen’s, then the oxidation of an alcohol can be
said to involve the removal of one hydrogen from the –OH group of the alcohol and of a
second hydrogen from the carbon atom to which the –OH group is attached. The
oxidation of a primary alcohol can be written as:

HH
ll
R – C – OH + [O] R – C O + H2O
l
H
primary alcohol aldehyde

The oxidation of an alcohol requires the use of some oxidizing agent such as
KMnO4,K2Cr2O7, or CuO. However, for the sake of simplicity the oxidizing agent in the
reactions shown in this chapter is simply listed as [O], which stands for any substance
that will yield the oxygen needed for the reaction.

At the end of this module, the students must be able to:

1. Become familiar with the functional groups present in aldehydes, ketones, and
carboxylic acids
2. Write equations for the formation of aldehydes, ketones and acids 3.
Distinguish between hemiacetals and acetals and between hemiketals and ketals
4. Recognize the biologic importance of various aldehydes, ketones and acids
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LEARNING RESOURCES
https://www.khanacademy.org/science/class-12-chemistry
india/x6a5fb67b43bb54b9:aldehydes-ketones-and-carboxylic-acids
https://www.khanacademy.org/science/organic-chemistry/aldehydes
ketones/reactions-aldehydes-ketones-jay/v/formation-of-hemiacetals
https://www.khanacademy.org/science/organic-chemistry/aldehydes
ketones
https://www.khanacademy.org/science/organic-chemistry/aldehydes
ketones/reactions-aldehydes-ketones-jay/v/formation-of-acetals
PRE-COMPETENCY
The student will be assessed according to their knowledge about the functional
groups and chemical reaction.

DISCUSSION

ALDEHYDES

Preparation by Oxidation of Primary Alcohol

Recall that a primary alcohol has the –OH functional group bonded to a carbon with one
or no other carbon atom attached to it. The following equation represents the oxidation
of methyl alcohol (CH3OH), a primary alcohol.
HH

R – C – OH + [O] R – C O + H2O

H
methyl alcohol formaldehyde

Observe that during the oxidation one H was removed from the –OH group and another
H from the carbon atom attached (the only carbon in this compound). Water is one
product of this reaction; the other product is a new kind of compound called an
aldehyde.
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Chem 103 – Organic Chemistry
In this example, the product is called formaldehyde. The formula for formaldehyde can
also be written as HCHO.
The following reaction indicate the oxidation of ethyl alcohol (also a primary
alcohol).
HHHH

H – C – C – OH + [O] H – C – C O + [O]

HHH
ethyl alcohol acetaldehyde

The oxidation of ethyl alcohol, a primary alcohol, yields acetaldehyde, whose

formula can also be written as CH3CHO. (Acetaldehyde is partially responsible for the
damage to the liver in cirrhosis.) In general,

oxidation
Primary alcohol aldehyde
Aldehydes all have the –CHO (called a carbonyl) group at the end of the chain.
The general formula for an aldehydes is RCHO, which indicates that some aliphatic alkyl
group (R) is attached to a –CHO group at the end of the molecule.

Naming Aliphatic Aldehydes

As we have seen, the oxidation of methyl alcohol, a primary alcohol of one carbon
atom, yields an aldehyde of one carbon atom, HCHO, formaldehyde. The oxidation of
ethyl alcohol, a primary alcohol of two carbon atoms, yields an aldehyde of two carbon
atoms, HC3CHO, acetaldehyde. Note that the term aldehyde comes from the word
alcohol dehydrogenation.
The IUPAC names for all aldehydes end in –al. To name an aldehyde according to
the IUPAC system, take the name of the longest chain containing the aldehyde group,
drop the ending –e, and replace it with the ending –al. Thus the following aldehyde,
which contains four carbons, is called butanal.
 CH3 – CH2 – CH2 – CHO
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The aldehyde group is always at the end of the chain, at carbon 1, with that
number being understood and not written.

EXERCISE 6.1
Name the following compound.
Br
l
CH3 – CH – CH – CH – CH2 – CH2 – CH2 – CHO
ll
CH3 CH3

EXERCISE 6.2
1. Draw the structure of
a. 4,4-dichloro-2,3-dimethylpentanal.
b. 2,3-dichloropropanal
c. 3,5-dimethyloctanal
2. Name:

CH3
l
CH3 – CH – CH2 – CHO

Aromatic Aldehydes
Aromatic aldehydes have the general formula ArCHO, where Ar stands for an aromatic
ring. The simplest aromatic aldehyde is benzaldehyde, which consist pf an aldehyde
group attached to a benzene ring. Benzaldehyde is prepared by the mild oxidation of
toluene, as shown in equation (18-1). Note that the side chain, the methyl group, is
more susceptible to odixation than the fairly stable benzene ring.
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Benzaldehyde is a colorless, oily liquid with a cherry-almondlike odor. It is used in
the preparation of flavouring agents, perfumes, drugs, and dyes.
Vanillin occurs in vanilla beans and gives the particular taste and odor to vanilla
extract. It is also has an aldehyde structure. Cinnamic aldehyde (cinnamaldehyde) is
present in oil of cinnamon, an oil found in cinnamon bark. Both vanillin and cinnamic
aldehyde can be prepared synthetically, and both are used as flavouring agents.
Table 6.1 compares the IUPAC and common names for some simple aldehydes.

Uses of Aldehydes
Formaldehyde is a colorless gas with a very sharp odor. It is used in the
laboratory as a water solution containing about 40 percent formaldehyde. The 40
percent solution commonly known as formalin is an effective germicide for the
disinfection of excreta, rooms, and clothing. Formalin hardens protein, making it very
insoluble in water. It is used in embalming fluids and also as a preservative for biologic
specimens. Formaldehyde solution should not be used directly on a patient or even in
the room with a patient because of irritating fumes.
Formaldehyde and its oxidation product, formic acid, and primarily responsible for
the systematic toxicity of methyl alcohol.
Glutaraldehyde is superior to formaldehyde as a sterilizing agent and therefore is
replacing it in use. Glutaraldehyde does not have the disagreeable odor that
formaldehyde does, and it is less irritating to the eyes and skin.

Table 6.1 Comparison of the Names of Some Aldehydes

Condense Structural IUPAC Name Common Name
Formula

HCHO Methanal Formaldehype

CH3CHO Ethanal Acetaldehyde

 CH3 – CH2 – CHO Propanal Propionaldehyde

Chem 103 – Organic Chemistry

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CH3 – CH – CHO 2-Methylpropanal Isubutyraldehyde

CH3

Paraldehyde is formed by the polymerization (joining) of three molecules of

acetaldehyde. Paraldehyde depresses the central nervous system. It is used as a
hypnotic, a sleep procedure. Paraldehyde is also used in the treatment of alcoholism
(see following paragraph). In therapeutic dosages it is nontoxic; it does not depress
heart action or respiration. Its disadvantages are its disagreeable taste and its
unpleasant odor.
Acetaldehyde (ethanal) is responsible for many of the unpleasant odor of ethyl
alcohol consumption. The drug Antabuse, used to treat alcoholics, functions by
increasing the concentration of acetaldehyde in the body.
Another aldehyde, glyceraldehyde, is an important component in the metabolism
of carbohydrates.

Tests of Aldehydes
In general, aldehydes are good reducing agents. Laboratory tests for the
presence of aldehyde are based on their ability to reduce copper (II) (cupric) ions to
form copper (I) (cuprous) oxide. When aldehyde is heated wit Benedict’s or Fehling’s
solution or treated with a Clini-test tablet (All of which contain Cu2+ complex ion), a red
precipitate of copper (I) oxide (CU2O) is formed. This is actually the test for glucose
(sugar) in urine, since glucose is an aldehyde.
Another laboratory test for the presence of an aldehyde involve the use of Tollen’s
reagent, which contains an Ag+ complex ion. In thus test, the presence of an aldehyde
causes the formation of a bright, shiny mirror on the inside of the test tube; hence the
name “silver mirror test”.

Reactions of Aldehydes
Oxidation Aldehydes can be oxidized to form acids, a type of reaction that will be
discussed later in this chapter.
RCHO + [O] RCOOH
aldehyde acid
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Chem 103 – Organic Chemistry
Note that this type of oxidation involves the addition of an oxygen atom.
Reduction Aldehydes can be reduced to the corresponding primary alcohols.
RCHO + [H] RCH2OH
aldehyde primary alcohol

This is the reverse of the reaction whereby a primary alcohol was oxodized to yield an
aldehyde.

aldehyde primary alcohol

CH3CHO + [H] CH3CH2OH
ethanal ethanol (ethyl
(acetaldehyde alcohol)
)

Biologic oxidation-recution in the body is carried out by substnaces called

coenzymes. One coenzyme, nicotinamide adenine dinucleotide (NAD+) acts as an
oxidizing agent and in turn is reduced to nicotinamide adenine dinucleotide hydride
(NADH), as shown in the following reaction:

NAD+ + CH3CH2OH NADH + CH3CHO + H+

oxidized from ethyl alcohol reduced from
of coenzyme of coenzyme
KETONES acetaldehyde

Preparation by Oxidation of a Secondary Alcohol

 Recall that a secondary alcohol is one in which the –OH group is bonded to a carbon
atom that is also bonded to two carbon atoms. Isopropyl alcohol is an example of a
secondary alcohol. The oxidation of isopropyl alcohol is indicated by the equaton H
isopropyl alcohol
(2-propanol)
CH3 – C – CH3

OH
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Chem 103 – Organic Chemistry

CH3 – C – CH3 + [O] CH3 – C – CH3 + H2O
isopropyl alcohol acetone
(2-propanol) (propanone)

As before, the oxygen atom from the oxidizing agent reacts with the H from the –OH
group and with the H attached to the same carbon as the –OH group, forming water and
a new class of compounds called ketones.
H

R–CO
aldehyde

The oxidation of a secondary alcohol yields a ketone, of the general formula RCOR. That
is, a ketone has two alkyl groupds attached to a C = O, carbonyl, group. This is
carbonyl group is present in both aldehyde and ketones. However, the carbonyl group is
the end of the chain in an aldehyde and not at the end in a ketone. R – C – R

O
ketone

Aromatic ketones have the general formula ArCOAr’ or ArCOR. The simplest
aromatic ketones is acetophenone.
Acetophene has been used as a hypnotic but has been supplanted for this
purpose by newer and safer drugs.
 Chloracetophenone is a *lacrimator and is used as a tear gas.
Among the aromatic ketone in the body are the sex hormones estrone,
progestone, testotsterone, and androsterone.
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Chem 103 – Organic Chemistry

Naming Aliphatic Ketones
In the IUPAC system, the names of ketones end in –one. To name a ketone according
to this system, take the name of the longest alkane containing the carbonyl group, drop
the ending –e, and add –one. Thus, the four-carbon ketone is calle butanone.
In the common system for naming ketones, each alkyl group attached to the
carbonyl group is named and the word ketone is added afterward. Thus, the name of
the preceeding compound, according to the common system, is methyl ethyl ketone,
since there is a methyl group attached to one end of the carbonyl group and an ethyl
group attached to the other end.

EXERCISE 6.3
Name the following compound using both IUPAC and common
systems. CH3 – CH2 – C – CH2 – CH2 – CH3
ll
O

EXERCISE 6.4
Name the following compound using both IUPAC and common
systems. Cl
l
CH3 – C – CH2 –C – CH3
l ll
Cl O

EXERCISE 6.5
Draw the structure of 2,2-dimethyl-1-pentanone.
 EXERCISE 6.6
Draw the structure of methylethylketone.
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Chem 103 – Organic Chemistry

Uses of Ketones
Acetone (propanone) is the simplest keotone. Acetone is a good solvent for fats
and oils. It is also frequently used in fingernail polish and in polish remover. Acetone is
normally present in small amounts in the blood and urine. In diabetes mellitus it is
present in larger amounts in the blood and urine and even in the expired air (see page
483). Dihydroxyacetone is an intermidiate in carbohydrate metabolism.
O

HO – CH2 – C – CH2 – OH
dihydroxyacetone

Reactions of Ketones
What happens when a ketone is oxidized? Consider the formula for the ketone acetone.
There are no hydrgen atoms on the carbon atom of the carbonyl group. Therefpre,
ketones are not easily oxidized. They are normally unreactive. Ketones can be reduced,
however, to the corresponding secondary alcohol. Ketones give a negative test with such
oxidizing agent as Benedict’s solution or Clini-test tablets. Recall that aldehydes give a
positive test with these reagents.
The test for acetone and ketone bodies makes use of the reaction between
sodium nitroprusside and ketones or ketone bodies to produce a lavender color.

CH3 – C – CH3
O
acetone
HEMIACETALS AND HEMIKETALS

The reaction of an aldehyde or a ketone with an alcohol yields compounds known

as *hemiacetals or *hemiketals, respectively.
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Chem 103 – Organic Chemistry

H H l l R – C O + R’OH R – C – OH

aldehyde alcohol l

OR’

hemiacetal

OR’’
l
R – C R + R’’OH R – C – OH
ll l alcohol

O OH
hemiketal
ketone

These types of compounds are important in discussing the structures of

monosaccharides.
If a hemiacetal or hemikal reacts with a second molecule of alcohol, an *acetal or
*ketal, respectively, is formed. These structures are important in disaccharides and
polysaccharides.

HH
 ll
R – C OH + R’OH R – C – OR’’ + H2O
ll
OR’ OR’
hemiacetal acetal
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Chem 103 – Organic Chemistry

OR’’ OR’’
ll
R – C – R’ + R’’'OH R – C – R’ + H2O
ll
OH OR’’

hemiketal ketal

ORGANIC ACIDS

Preparation by Oxidation of an Aldehyde

The oxidation of a primary alcohol yield an aldehyde. Aldehyde in turn can be
easily oxidized. When an aldehyde is oxidized, the reaction is
H OH
ll
acetaldehyde acetic acid
CH3 C O + [O] CH3C O
(also written as CH3COOH)

The resulting compound is acidic becauseit yield hydrogen ions in solution. (Note
that thisreaction involves oxidation because of a gain in oxygen ; see Section 6-2).

The functional group of an organic acid is –COOH, so the oxidation of an

aldehyde to an acid can be written functionally as

[O]
R –CHO R – COOH
aldehyde acid

[O]

ArCHO R –ArCOOH
aldehyde acid
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Chem 103 – Organic Chemistry

The oxidation of methyl alcohol, a primary alcohol, to an aldehyde and then to an
acid is illustrated in the following euqation.
H
l
[O] [O] H H OH
H–C–OH–COH–CO lll
(also written as HCOOH)
(methanol)
formaldehyde
(methanal)
formic acid
methyl alcohol (methanoic acid)

Primary alcohols can be also be oxidized directly to acids.

[O]
CH3CH2OH CH3C O
acetic acid (ethanoic acid)
ethyl alcohol
(ethanol)

Naming Organic Acids

The IUPAC names for organic acids end in –oic acid. To name an acid according
to the IUPAC system, take the longest alkane containing the acid group, frop the ending
–e and add –oic acid. Thus, formula (18-2) shows ethanoic acid.
The common names of acids are derived fom the name of the aldehyde from
which they may be prepared. Thus, formula (18-2) shows ethanoic acid.
The common names of acids are derived from the names of the aldehyde from
which they may be prepared. Thus, formula (18-2), derived from acetaldehyde, is called
acetic acid.
The generall formula for an acid is RCOOH or ArCOOH. All organic acids contain
at least one –COOH group. This group is called the carboxyl group, and it is this group
that yields hydrogen ions.
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Table 6-2 Some Common Dicarboxylic Acids
Structure Common Name IUPAC Name

COOH Oxalic Acid Ethanedioic acid

COOH

COOH Malonic Acid Propanedioic acid

CH2
COOH

COOH Succinic Acid Butanedioic acid

CH2
CH2
COOH

Organic acids containing two carboxyl groups are called dicarboxylix acids. Those
containing three carboxyl groups are called tricarboxyicl acids. Table 18-2 gives the
names and structure of some common dicarboxylic acids.
 EXERCISE 6.7
Name the following compound

CH3 – CH2 – CH2 – CH2 – COOH

l
Cl

EXERCISE 6.8
Draw the structure for 3 – chlorobenzoic acid.

Properties and Reactions of Organic Acids

Most organc acids are relatively weak acids since they ionize only slightly in water.

CH3COOH H+ CH3COO

acedic acid hydrogen

(ion)

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Chem 103 – Organic Chemistry
acetate ion
Organic acids react with the bases to form salts and water. The general reaction of an
organic acid with a base to form a salt and water can be written as follows:

RCOOH + NaOH RCOON2 + H2O

organic acid base water

oraganic salt

CH3COOH + NaOH CH3COONa + H2O

acetic acid sodium water (a
sodium hydroxidesalt) water

Organic acids also react with bicarbonates and carbonates.

 sodium carbonate
CH3COOH + NaHCO3 CH3COONa + CO2(g) + H2O acetic acid
sodium acetate

2 HCOOH + Na2CO3 2 HCOONa + CO2(g) + H2O formic acid sodium carbonate

sodium acetate

Organic acids containing few carbon atoms are soluble in water. As the length of
the carbon chain increases, the solubility in water decreases.
Organic acids aalso react with alcohols to form a class of compounds called
esters, which will be dealt with in the next chapter.

Medically Important Organic Acids

Formic acid (HCOOH) is a colorless liquid with a sharp, irritating odor. Formic acid
is found in the string of bees and ants and causes the characteristic pain and swelling
when it is injected into the tissues. It is one of the strongest organic acids.
Acetic acid (CH3COOH) is one of the components of vinegar, where it is usually
found as a 4 to 5 percent solution. Acetic acid can be made by the oxidation of ethyl
alcohol. The acetyl group,
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Chem 103 – Organic Chemistry
O
ll
CH3C –
derive from acetic acid, is very important in metabolic reactions.
Citric acid found in citrus fruits. Its formula indicates that it is an alcohol as well
as an acid. Citric acid contains one alcohol (–COOH) groups. It is an example of a
tricarboxylic acid.
Magnesium citrate, a salt of citric acid, is used as a catharic (a medication for
stimulating the evacuation of the bowels). Sodium citrate, another salt of citric acid, is
used as a blood anticoagulant. (It removes Ca2+ needed for a coagulation form the
blood.)
Lactic acid is found in sour milk. It is formed in the fermentation of milk sugar,
lactose. Its formula is
HH
ll
H – C – C – COOH
ll
H OH

lactic acid

Lactic acid is also both an acid and an alcohol. It is formed whenever the body
produces energy anaerobically.
Oxalic acid is another one of the strong, naturally occuring orgaanic acids. Its
formula is shown in Table 6.2. Oxalic acid is used to remove stains, particularly rust and
potassium permanganate stains, from clothing. It is poisonous when taken internally.
Oxalate salts also prevent clotting by *chelating Ca2+ from the blood. However, oxalate
can be used only for blood samples that are to be analyzed in the laboratory because
these salts are poisonous and cannot be added directly to the bloodstream.
Pyruvic acid is produced during the anerobic phase of oxidation of glucose. It is a
keto acid. In muscle, pyruvic acid is reduced to lactic acid during anerobic exercise. In
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the tissues, pyruvic acid is changed to acetyl coenzyme A, which then enters the Krebs
cycle.
Tartaric acid is another organic acid that iis both an acid and an alcohol. Tartaric
acid is found in several fruits, particularly grapes. Potassium hydrogen tartrate, an acid
salt called cream of tartar, is used in making baking powders. Rochelle salts, or
potassium sodium tartrate, is used as a mild cathartic.
Stearic acid is solid greaselike acid that is insoluble in water. It is an example of a
fatty acid. Its formula is C17H35COOH. The sodium salt of stearic acid, sodium stearate, is
a commonly used soap.
C17H35COOH + NaOH C17H35COONa + H2O
stearic acid
sodium stearate

Benzoic Acid
Benzoic acid can be produced by the oxidation of benzaldehyde or by the
oxidation of toluene.
Benzoic acid is a white crytalline compound that is slightly soluble in cold water
and moe soluble in hot water. It is used medicinally as an antifungal agent. The sodium
salt of benzoic acid, sodium benzoate, is used as a preservative.
Salicylic acid is both an alcohol and an acid, as can be seen from its structure.
Salicylic acid is a white crystalline compound with properties similar to those of benzoic
acid. It is used in the treatment of fungal infections and also for the removal of warts
and corns.
Commonly used compounds of salicylic acid area the salt sodium salicylate and
the ester methyl salicylate (see the following chapter).
Sodium salicylate is used an *antipyretic (to reduce fever) and also to relieve pain
of arthritis, bursitis, and headache. Methyl salicylate is a liquid with a pleasant odor, that
of wintergreen. It is used topically relieve pain in muscles and joints.
The acetyl derivative of salicylic acid (the acetyl group is CH3CO –) is
acetylsalicylic acid, more commonly known as aspirin. Aspirin is used as an *analgesic;
as an antipyretic; for the treatment of colds, headaches, minor aches, and pains; and as
a mild blood
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Chem 103 – Organic Chemistry
thinner, especially for individuals who have had a coronary artery bypass. Aspirin is lso
used in the treatment of theumatic fever. Morethan 50 tons of aspirin tablets are used
daily in the United States. Use of aspirin is contraindicated after surgery because it
interferes with normal blood clotting and can induce hemorrhagingl. Aspirin can also
cause bleeding of the stomach and therefore should not be taken on an “empty”
stomach. One person in 10,000 is allergic to aspirin.
 The action of aspirin is related directly to that of the prostaglandins. Aspirin
stimulates respiration directly, and overdose can cause serious acidebase nbalance
disturbance.
Evidence appears to indicate that aspirin can prevent blood clots fromforming by
interfering with the action of the blood platelets. There is also evidence that one aspirin
every other day helps prevent heart attacks.
Acetaminophen (Tylenol) has been used as a substitute for aspirin because it
does not cause gastrointestinal bleeding and does not affect blood clotting. However,
overdose can lead to hepatic damage, can be the case with aspirin itself. It is not
effective against inflammation.

Chem 103 – Organic Chemistry

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