Alcohols,

Phenols and
Thiols
BONDING CHARACTERISTICS OF OXYGEN ATOMS IN ORGANIC
COMPOUNDS
Alcohols

• An alcohol is an organic compound in which

an —OH group is bonded to a saturated
carbon atom.
• A saturated carbon atom is a carbon atom
that is bonded to four other atoms.
Alcohol

•The —OH group, the

functional group that is
characteristic of an alcohol,
is called a hydroxyl group.
NOMENCLATURE FOR
ALCOHOLS

• Common names exist for

alcohols with simple
(generally C1 through C4)
alkyl groups. To assign a
common name:
• Rule 1: Name all of the
carbon atoms of the
molecule as a single alkyl
group.
• Rule 2: Add the word
alcohol, separating the
words with a space.
 NOMENCLATURE FOR ALCOHOLS
• IUPAC rules for naming alcohols that contain a single
hydroxyl group
• Rule 1: Name the longest carbon chain to which the
hydroxyl group is attached. The chain name is obtained
by dropping the final -e from the alkane name and
adding the suffix -ol.
• Rule 2: Number the chain starting at the end nearest the
hydroxyl group, and use the appropriate number to
indicate the position of the —OH group. (In numbering
of the longest carbon chain, the hydroxyl group has
priority over double and triple bonds, as well as over
alkyl, cycloalkyl, and halogen substituents.)
 • Rule 3: Name and locate any other
substituents present.
• Rule 4: In alcohols where the —OH
group is attached to a carbon atom in
a ring, the hydroxyl group is assumed
NOMENCLATURE to be on carbon 1. Numbering then
proceeds in a clockwise or
FOR ALCOHOLS counterclockwise direction to give the
next substituent the lower number.
The number “1” is omitted from the
name since by definition the
hydroxyl-bearing carbon is carbon 1.
Practice
 Alcohols with More Than
One Hydroxyl Group

• Polyhydroxy alcohols —
alcohols that possess more
than one hydroxyl group
• An alcohol in which two
hydroxyl groups are present
is named as a diol, one
containing three hydroxyl
groups is named as a triol,
and so on. In these names
for diols, triols, and so forth,
the final -e of the parent
alkane name is retained for
pronunciation reasons.
 •Six commonly encountered
alcohols: methyl, ethyl, and
IMPORTANT
isopropyl alcohols (all
COMMONLY
monohydroxy alcohols),
ENCOUNTERED
ethylene glycol and
ALCOHOLS
propylene glycol (both
diols), and glycerol (a triol).
Methyl Alcohol (Methanol)
Methyl alcohol, with one carbon atom and one —OH group, is the simplest alcohol

This colorless liquid is a good fuel for internal combustion engines. (Methyl alcohol fires are
easier to put out than gasoline fires because water mixes with and dilutes methyl alcohol.)

Methyl alcohol also has excellent solvent properties, and it is the solvent of choice for paints,
shellacs, and varnishes.

Methyl alcohol is sometimes called wood alcohol, terminology that draws attention to an early
method for its preparation—the heating of wood to a high temperature in the absence of air.
Methyl Alcohol (Methanol)
Drinking methyl alcohol is very dangerous. Within the human body,
methyl alcohol is oxidized by the liver enzyme alcohol dehydrogenase
to the toxic metabolites formaldehyde and formic acid.

Formaldehyde can cause blindness (temporary or permanent). Formic

acid causes acidosis
Ethyl Alcohol (Ethanol)
Ethyl alcohol, the two-carbon monohydroxy alcohol, is the alcohol present in alcoholic
beverages and is commonly referred to simply as alcohol or drinking alcohol.

Like methyl alcohol, ethyl alcohol is oxidized in the human body by the liver enzyme
alcohol dehydrogenase.

Acetaldehyde, the first oxidation product, is largely responsible for the symptoms of
hangover.

Ethyl alcohol oxidation products are less toxic than those of methyl alcohol
 Ethyl Alcohol
(Ethanol)
• Long-term excessive use of ethyl
alcohol may cause undesirable
effects such as cirrhosis of the liver,
loss of memory, and strong
physiological addiction
• Links have also been established
between certain birth defects and
the ingestion of ethyl alcohol by
women during pregnancy (fetal
alcohol syndrome).
 Ethyl Alcohol
(Ethanol)
• Ethyl alcohol can be produced by yeast
fermentation of sugars found in plant extracts
• The synthesis of ethyl alcohol in this manner,
from grains such as corn, rice, and barley, is the
reason why ethyl alcohol is often called grain
alcohol.
• Denatured alcohol is ethyl alcohol that has been
rendered unfit to drink by the addition of small
amounts of toxic substances (denaturing agents).
Almost all of the ethyl alcohol used for industrial
purposes is denatured alcohol.
 Isopropyl Alcohol (2-Propanol)

Isopropyl alcohol’s rapid Isopropyl alcohol has

A 70% isopropyl a bitter taste. Its Large amounts (about 150
evaporation rate creates
alcohol–30% water toxicity is twice that mL) of ingested isopropyl
a dramatic cooling effect
solution is marketed as of ethyl alcohol, but it alcohol can be fatal; death
when it is applied to the
rubbing alcohol. causes few fatalities occurs from paralysis of the
skin, hence its use for
because it often central nervous system.
alcohol rubs to combat
high body temperature. induces vomiting and
thus doesn’t stay
down long enough to
be fatal
 Ethylene Glycol (1,2-
Ethanediol) and Propylene
Glycol (1,2-Propanediol)

• Ethylene glycol and

propylene glycol are the
two simplest alcohols
possessing two —OH
groups.
• Besides being diols, they
are also classified as
glycols. A glycol is a diol
in which the two —OH
groups are on adjacent
carbon atoms.
 Ethylene Glycol (1,2-Ethanediol) and Propylene
Glycol (1,2-Propanediol)
• Both of these glycols are colorless, odorless, high-boiling liquids
that are completely miscible with water. Their major uses are as
the main ingredient in automobile “year-round” antifreeze and
airplane “de-icers”.
• Ethylene glycol is extremely toxic when ingested. In the body, liver
enzymes oxidize it to oxalic acid. Oxalic acid, as a calcium salt,
crystallizes in the kidneys, which leads to renal problems.
• Propylene glycol, on the other hand, is essentially nontoxic and has
been used as a solvent for drugs.
 Glycerol (1,2,3-
Propanetriol)

• Glycerol, which is
often also called
glycerin, is a clear,
thick liquid that has
the consistency of
honey. Its molecular
structure involves
three —OH groups
on three different
carbon atoms.
Glycerol (1,2,3-Propanetriol)
Glycerol is normally present in the human body because it is a product of fat metabolism.

It is present, in combined form, in all animal fats and vegetable oils

In some Arctic species, glycerol functions as a “biological antifreeze”

Because glycerol has a great affinity for water vapor (moisture), it is often added to pharmaceutical preparations
such as skin lotions and soap.

Florists sometimes use glycerol on cut flowers to help retain water and maintain freshness.

Its lubricative properties also make it useful in shaving creams and in applications such as glycerol suppositories for
rectal administration of medicines
 CLASSIFICATION OF
ALCOHOLS
• Alcohols are classified as primary (1°),
secondary (2°), or tertiary (3°) depending
on the number of carbon atoms bonded
to the carbon atom that bears the
hydroxyl group.
• A primary alcohol is an alcohol in which
the hydroxyl-bearing carbon atom is
bonded to only one other carbon atom.
• A secondary alcohol is an alcohol in
which the hydroxyl bearing carbon atom
is bonded to two other carbon atoms
• A tertiary alcohol is an alcohol in which
the hydroxyl-bearing carbon atom is
bonded to three other carbon atoms
CHEMICAL REACTIONS
OF ALCOHOLS
 •Hydrocarbons of all types
undergo combustion in air to
produce carbon dioxide and
water. Alcohols are also
Combustion flammable; as with
hydrocarbons, the
combustion products are
carbon dioxide and water.
 Intramolecular Alcohol
Dehydration
A dehydration reaction is a chemical reaction in which the
components of water (H and OH) are removed from a single reactant
or from two reactants (H from one and OH from the other).

In intramolecular dehydration, both water components are removed

from the same molecule.
 Intramolecular
Alcohol Dehydration

• Reaction conditions for

the intramolecular
dehydration of an
alcohol are a
temperature of 180 °C
and the presence of
sulfuric acid as a
catalyst. The
dehydration product is
an alkene.
 Intramolecular
Alcohol Dehydration

• Intramolecular alcohol
dehydration is an example of
an elimination reaction
• An elimination reaction is a
reaction in which two groups
or two atoms on neighboring
carbon atoms are removed,
or eliminated, from a
molecule, leaving a multiple
bond between the carbon
atoms.
 Intermolecular Alcohol
Dehydration

• At a lower temperature (140 °C)

than that required for alkene
formation (180 °C), an
intermolecular rather than an
intramolecular alcohol dehydration
process can occur to produce an
ether—a compound with the
general structure R—O—R
• In such ether formation, two
alcohol molecules interact, an H
atom being lost from one and an —
OH group from the other. The
resulting “leftover” portions of the
two alcohol molecules join to form
the ether.
Intermolecular Alcohol Dehydration

The preceding reaction is an example of condensation. A condensation

reaction is a chemical reaction in which two molecules combine to form a
larger one while liberating a small molecule, usually water.

In this case, two alcohol molecules combine to give an ether and water.
 Halogenation
•Alcohols undergo halogenation
reactions in which a halogen atom is
substituted for the hydroxyl group,
producing an alkyl halide.
 STRUCTURAL
CHARACTERISTICS OF
PHENOLS

• A phenol is an
organic compound
in which an —OH
group is attached to
a carbon atom that
is part of an
aromatic carbon
ring system.
 The general formula for phenols is
Ar–OH, where Ar represents an aryl
group.

An aryl group is an aromatic carbon

Phenols ring system from which one
hydrogen atom has been removed.

A hydroxyl group is thus the

functional group for both phenols
and alcohols
 NOMENCLATURE FOR
PHENOLS

• Besides being the

name for a family of
compounds, phenol
is also the IUPAC-
approved name for
the simplest member
of the phenol family
of compounds.
 NOMENCLATURE FOR
PHENOLS

• The IUPAC rules for naming phenols

are simply extensions of the rules
used to name benzene derivatives
with hydrocarbon or halogen
substituents.
• The parent name is phenol.
• Ring numbering always begins with
the hydroxyl group and proceeds in
the direction that gives the lower
number to the next carbon atom
bearing a substituent. The numerical
position of the hydroxyl group is not
specified in the name because it is 1
by definition.
 Methyl and hydroxy Methylphenols are called
derivatives of phenol have cresols. The name cresol applies
IUPAC-accepted common to all three isomeric
NOMENCLATURE names. methylphenols.

FOR PHENOLS
NOMENCLATURE
FOR PHENOLS

For hydroxyphenols,
each of the three
isomers has a
different common
name.
 Phenols are generally low-melting
solids or oily liquids at room
temperature. Most of them are only
slightly soluble in water.
PHYSICAL
AND Many phenols have antiseptic and
disinfectant properties. The simplest
CHEMICAL phenol, phenol itself, is a colorless
solid with a medicinal odor.
PROPERTIES
OF PHENOLS Its melting point is 41°C, and it is
more soluble in water than are most
other phenols
 Both alcohols and phenols are
flammable.

Alcohols vs Dehydration is a reaction of alcohols

but not of phenols; phenols cannot
Phenols be dehydrated.

Both alcohols and phenols undergo

halogenation in which the hydroxyl
group is replaced by a halogen atom
in a substitution reaction.
OCCURRENCE OF AND USES
FOR PHENOLS

• Dilute (2%) solutions of

phenol have long been used
as antiseptics. Concentrated
phenol solutions, however,
can cause severe skin burns.
• Today, phenol has been
largely replaced by more
effective phenol derivatives
such as 4-hexylresorcinol. The
compound 4-hexylresorcinol is
an ingredient in many
mouthwashes and throat
lozenges.
 OCCURRENCE OF
AND USES FOR
PHENOLS
• The phenol derivatives
o-phenylphenol and 2-
benzyl-4-chlorophenol
are the active
ingredients in Lysol, a
disinfectant for walls,
floors, and furniture in
homes and hospitals.
 OCCURRENCE OF AND USES FOR
PHENOLS

• A number of phenols possess antioxidant activity.

• An antioxidant is a substance that protects other
substances from being oxidized by being oxidized
itself in preference to the other substances.
• A naturally occurring phenolic antioxidant that is
important in the functioning of the human body is
vitamin E.
OCCURRENCE OF AND USES FOR PHENOLS
A number of phenols found in plants are used as flavoring agents and/or antibacterials.

Thymol, obtained from the herb thyme, possesses both flavorant and antibacterial
properties. It is used as an ingredient in several mouthwash formulations.

Eugenol is responsible for the flavor of cloves. Dentists traditionally used clove oil as an
antiseptic because of eugenol’s presence.

Vanillin, which gives vanilla its flavor, is extracted from the dried seed pods of the vanilla
orchid.
 SULFUR ANALOGS OF
ALCOHOLS

• Many organic compounds

containing oxygen have sulfur
analogs, in which a sulfur atom has
replaced an oxygen atom.
• Thiols, the sulfur analogs of
alcohols, contain —SH functional
groups instead of —OH functional
groups. The thiol functional group
is called a sulfhydryl group. A
sulfhydryl group is the —SH
functional group
• A thiol is an organic compound in
which a sulfhydryl group is bonded
to a saturated carbon atom. An
older term used for thiols is
mercaptans.
 Nomenclature for Thiols

• Thiols are named in the

same way as alcohols in the
IUPAC system, except that
the –ol becomes -thiol. The
prefix thio- indicates the
substitution of a sulfur atom
for an oxygen atom in a
compound
• As in the case of diols and
triols, the -e at the end of
the alkane name is also
retained for thiols.
 Nomenclature for Thiols

• Common names for

thiols are based on
use of the term
mercaptan, the older
name for thiols. The
name of the alkyl
group present (as a
separate word)
precedes the word
mercaptan.
Practice
1.

2.
 Properties of Thiols
Two important properties of thiols are lower boiling points than alcohols of
similar size (because of lack of hydrogen bonding) and a strong, disagreeable
odor.

The familiar odor of natural gas results from the addition of a low concentration
of methanethiol (CH3—SH) to the gas.

The exceptionally low threshold of detection for this thiol enables consumers to
smell a gas leak long before the gas, which is itself odorless, reaches dangerous
levels.