CHEM (FINALS)
suffix -ol.
WEEK 13: ALCOHOLS, ETHERS, PHENOLS,
THIOLS
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.
- 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.
 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
 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
to be on carbon 1. Numbering then
proceeds in a clockwise or
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.
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.
IMPORTANT COMMONLY ENCOUNTERED
ALCOHOLS
 Six commonly encountered alcohols: methyl,
ethyl, and isopropyl alcohols (all
monohydroxy alcohols), ethylene glycol and
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.
 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
 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 can be produced by yeast
fermentation of sugars found in plant
extracts.
ISOPROPYL ALCOHOL (2-Propanol)
 A 70% isopropyl alcohol–30% water
solution is marketed as rubbing alcohol.
 Isopropyl alcohol’s rapid evaporation rate
creates a dramatic cooling effect when it is
applied to the skin, hence its use for alcohol
rubs to combat high body temperature.
 Isopropyl alcohol has a bitter taste. Its
toxicity is twice that of ethyl alcohol, but it
causes few fatalities because it often induces
vomiting and thus doesn’t stay down long
enough to be fatal.
 Large amounts (about 150 mL) of ingested
isopropyl alcohol can be fatal; death occurs
from paralysis of the central nervous system.
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.
 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 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
Combustion - Hydrocarbons of all types undergo
combustion in air to produce carbon dioxide and
water. Alcohols are also
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
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.
  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.
 T
he 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.
PHENOLS
 The general formula for phenols is
Ar–OH, where Ar represents an aryl group.
 An aryl group is an aromatic carbon 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.
 The IUPAC rules for naming phenols
are simply extensions of the rules
used to name benzene derivatives
with hydrocarbon or halogen
substituents.
 The parent’s 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 derivatives of phenol
have IUPAC-accepted common names.
 Methylphenols are called cresols. The name
cresol applies to all three isomeric
methylphenols.
 For hydroxyphenols, each of the three
isomers has a different common name.
PHYSICAL AND CHEMICAL PROPERTIES
OF PHENOLS
 Phenols are generally low-melting
solids or oily liquids at room
temperature. Most of them are only
slightly soluble in water.
 Many phenols have antiseptic and
disinfectant properties. The simplest
phenol, phenol itself, is a colorless
solid with a medicinal odor.
 Its melting point is 41°C, and it is
more soluble in water than are most
other phenols.

ALCOHOLS VS PHENOLS
 Both alcohols and phenols are
flammable.
 Dehydration is a reaction of alcohols but not
of phenols; phenols cannot be dehydrated.
 Both alcohols and phenols undergo
halogenation in which the hydroxyl group is
replaced by a halogen atom in a substitution
reaction.
SULFUR ANALOGS OF ALCOHOL
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.
 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.
 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.

 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.

NOMENCLATURE OF 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
A number of phenols possess antioxidant activity. substitution of a sulfur atom
 An antioxidant is a substance that protects for an oxygen atom in a
other substances from being oxidized by compound.
being oxidized itself in preference to the  As in the case of diols and triols, the -e at the
other substances. end of the alkane name is also retained for
 A naturally occurring phenolic antioxidant thiols.
that is important in the functioning of the
human body is vitamin E.

 A number of phenols found in plants are

used as flavoring agents and/or
antibacterials.
  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.

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.
  Aliphatic ketones are named substitutively by
replacing the final -e of the name of the
corresponding alkane with -one.
 The chain is then numbered in the way that
gives the carbonyl carbon
atom the lower possible number, and this
number is used to
designate its position.
WEEK 14: ALDEHYDES AND KETONES
 Aldehydes have a carbonyl group bonded to
a carbon atom on one side and a hydrogen
atom on the other side. (Formaldehyde is an
exception because it has hydrogen atoms on
both sides.)
 Some ketones have common names that are
 Ketones have a carbonyl group bonded to retained in the IUPAC system:
carbon atoms on both
sides.

PHYSICAL PROPERTIES
 The carbonyl group is a polar group;
therefore, aldehydes and
ketones have higher boiling points than
hydrocarbons of the same
molecular weight.
 Aldehydes and ketones cannot have strong
NOMENCLATURE OF ALDEHYDES AND hydrogen bonds between
KETONES their molecules, they have lower boiling
 Aliphatic aldehydes are named substitutively points than the
in the IUPAC system by replacing the final -e corresponding alcohols.
of the name of the corresponding alkane with
-al.
 Since the aldehyde group must be at an end
of the carbon chain, there is no need to
indicate its position.
 Common names are derived from the
common names for the corresponding
carboxylic acids, and some of them are
retained by the IUPAC as acceptable names.  The carbonyl oxygen atom allows molecules
of aldehydes and
ketones to form strong hydrogen bonds to
molecules of water. As a
result, low-molecular-weight aldehydes and
ketones show appreciable solubilities in
water.

 Aldehydes in which the iCHO group is

attached to a ring system are named
substitutively by adding the suffix
carbaldehyde.
THE CHEMISTRY OF ALDEHYDES & KETONES
 Many aldehydes and ketones have pleasant
fragrances and, because
of this, they have found use in perfumes.
 With the development of synthetic organic
chemistry in the
nineteenth century, many ingredients now
used in perfumes result
from the creativity of laboratory chemists.
SYNTHESIS OF ALDEHYDES
Aldehydes by Oxidation of 18 Alcohols
 The oxidation state of an aldehyde lies
between that of an 18 alcohol and a
carboxylic acid.
 Aldehydes can be prepared from 18 alcohols
by the Swern oxidation
and oxidation with pyridinium chlorochromate
(C5H5NHCrO3Cl-, or
PCC)
 The following are examples of the use of the
Swern oxidation and
PCC in the synthesis of aldehydes.
Aldehydes by Ozonolysis of Alkenes
 Alkenes can be cleaved by ozonolysis of
their double bond. The products are
aldehydes and ketones.
Aldehydes by Reduction of Acyl Chlorides, Esters,
and Nitriles
 Theoretically, it is possible to prepare
aldehydes by reduction of
carboxylic acids.
 In practice, this is not possible with the
reagent normally used to
reduce a carboxylic acid, lithium aluminum
hydride (LiAlH4 or LAH).
 When any carboxylic acid is treated with
LAH, it is reduced all the way to the
1*alcohol.
 This happens because LAH is a very
powerful reducing agent and aldehydes
are very easily reduced.
 Acyl chlorides (RCOCl), esters (RCO2R9),
and nitriles (RCN) are all easily prepared
from carboxylic acids (Chapter 17), and they
all are more easily reduced.
 The following scheme summarizes how
lithium tri-tert butoxyaluminum hydride and
DIBAL-H can be used to synthesize
aldehydes from acid derivatives:
Aldehydes from Acyl Chlorides: RCOCl ----> RCHO
 Acyl chlorides can be reduced to aldehydes
by treating them with
LiAlH[OC(CH3)3]3, lithium tri-tert-
butoxyaluminum hydride, at -78 8C.
 Carboxylic acids can be converted to acyl
chlorides by using SOCl2.
SYNTHESIS OF KETONES
We have seen three laboratory methods for the
preparation of ketones in earlier chapters:
1. Ketones (and aldehydes) by ozonolysis of
alkenes
 2. Ketones from arenes by Friedel–Crafts
acylations

KETONES FROM NITRILES

 Treating a nitrile (R-Ci≡N) with either a

Grignard reagent or an
organolithium reagent followed by hydrolysis
yields a ketone.

WEEK 15: CARBOXYLIC ACIDS, ESTERS, AND

OTHER ACID

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.
 Carboxylic acids have the following general
formula:
  Some simple carboxylic acids:

 Since carbon can have only have four bonds,

there are no cyclic carboxylic
acids (i.e. the carboxyl group can not form
part of a carbon ring.

 The following molecules have a similar

structure to carboxylic acids

IUPAC

nomenclature for carboxylic acids

Dicarboxylic acids:
 For these compounds, both ends of a chain
 For monocarboxylic acids (one –COOH will end with a –COOH group. The
group): parent chain is the one that involves both –
 Select the longest, continuous carbon chain COOH groups.
that involves the carboxyl group.  The parent chain is named as an alkane and
This is the parent chain and the –COOH the term “dioic acid” is added
carbon is designated as C-1 afterwards to indicate the diacid structure.

Common names for carboxylic acids:

 For common names carboxylic acids and

diacids, substituents are often numbered
using a Greek system:

  Name  So, the following molecule could be called α-

the Methylpropionic acid (or, using the IUPAC
parent system, 2-Methylpropanoic acid)
chain by
dropping Polyfunctional carboxylic acids (Unsaturated
the “e” acids)
from the

corresponding alkane
name and changing to “oic acid”
 Indicate the identity and location of
substituents on the parent chain at the
front of the carboxylic acids name.
  Unsaturated acids possess a unit of
unsaturation (double/triple C-C bond) in the
structure. Most common unsaturated acids:
Physical Properties of Carboxylic acids
 Carboxylic acids are the most polar
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-
Preparation of Carboxylic Acids
atom of the carbonyl group is treated as an
“oxo” substituent and the molecule is called
2-oxopropanoic acid
Preparation of Carboxylic Acids
Metabolic Carboxylic Acid
 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)
functional group so far. The presence of the
carbonyl group next to the OH causes the O-
H bond to be even more polar.
 Because of the very polar –COOH group,
carboxylic acids exhibit strong intermolecular
attractions.
 Carboxylic acids of a given number of carbon
atoms have a higher boiling point that
alcohols.
 They also tend to dimerize, producing
molecules that are twice as heavy which
have enhanced London forces (thus higher
boiling points)
 In terms of water solubility, because of H-
bonding, carboxylic acids dissolve well in
water (up to 4 carbon chains)
 Beyond 4 carbon chains, water solubility
drops off rapidly
 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
1. By oxidation of alkenes: alkenes can be
oxidized to carboxylic acids with hot alkaline
KMnO4:
 Alternatively, ozonides can be subjected to these can be hydrolyzed to α-hydroxy
an oxidative work up that acids. In the hydrolysis the -CN group is
yields carboxylic acids: converted to a -CO2H group.
2. By oxidation of aldehydes and primary
alcohols. General Reaction:
 Aldehydes can be oxidized to carboxylic
acids with mild oxidizing agents such as Ag
(NH3)2 +HO-

 Primary alcohols can be oxidized with Specific Examples:

KMnO4.
 Aldehydes and primary alcohols are oxidized
to carboxylic acids with chromic acid
(H2CrO4) in aqueous acetone (the Jones
oxidation)
6. By carbonation of Grignard reagents.
Grignard reagents react with carbon dioxide
to yield magnesium carboxylates.
Acidification produces carboxylic acids:

3. By
Acidity of carboxylic acids
 When carboxylic acids are placed in
water, they undergo de-protonation.

benzylic oxidation of alkylbenzenes.

 Primary and secondary alkyl groups (but
not 3o groups) directly attached to a
benzene ring are oxidized by KMnO4 to
a -CO2H group.

4. By oxidation of the benzene ring.

 The benzene ring of an alkylbenzene
can be converted to a carboxyl group by
ozonolysis, followed by treatment with
hydrogen peroxide

5. By hydrolysis of cyanohydrins and other

nitriles.
 Aldehydes and ketones can be
converted to cyanohydrins and that

Acidity of carboxylic acids
Carboxylic acid salts
 When carboxylic acid is reacted with
strong bases, they are converted to salts
as follows:
 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 medicine that possess
acid groups are
marketed as carboxylic acid salts (sodium,
potassium salts).
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:
 An ester consists of an acid portion and an
alcohol portion:
 Cyclic esters (lactones) are created from
hydroxy acids (bear both a
hydroxyl group and a carboxyl group) in an
intramolecular esterification reaction:
  Indicate the structures of the carboxylic acid Selected common Esters:
and alcohol that are needed to make an
ester:

 Flavor/fragrance agents
 Pheromones

Nomenclature of Esters
 IUPAC naming:
 1. the name for the alcohol portion comes
first: name the alkyl part of  Medications
the alcohol. Present the alkyl name separate
from the remainder of the ester name.  Synthesis of Aspirin
 2. the carboxylic portion is named as if it
were deprotonated, changing the “-ic acid” Isomerism in Carboxylic acids and Esters
part of the name to “ate”  Carboxylic acids and esters that have a
given number of carbon atoms form another

example of functional group isomers:

 For both carboxylic acids and esters, skeletal

isomers are possible:

 Positional isomers are possible for esters,

but not carboxylic acids.

Physical Properties of Esters

 Because they do not possess –OH groups,
esters cannot form H- bonds with other Ester
molecules. As a result, esters have lower
boiling point 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 reaction of Esters

 Ester Hydrolysis: the hydrolysis of an ester is
Other Examples: accomplished by reacting water with an ester
 in the presence of an acid catalyst (this is the
reverse of esterification)
 Ester Saponification: another hydrolysis
reaction but this time under basic conditions.
Rather than a carboxylic acid, the salt is
produced here.