1-octanol and 3-octanol, contribute to the distinctive flavor of mushrooms.

Normal bonding behavior for oxygen atoms in such functional groups is the formation
of two covalent bonds. Oxygen is a member of Group VIA of the periodic table and
thus possesses six valence electrons. To complete its octet by electron sharing, an
oxygen atom can form either two single bonds or a double bond.
Alcohols are the fi rst type of hydrocarbon derivative containing a single oxygen atom to
be considered. They have the generalized formula:

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. A hydroxyl group is the -OH functional group.
In the naming of alcohols with unsaturated carbon chains, two endings are needed:
one for the double or triple bond and one for the hydroxyl group. The -ol suffix
always comes last in the name; that is, unsaturated alcohols are named as alkenols
or alkynols.
Polyhydroxy alcohols—alcohols that possess more than one hydroxyl group
A hydroxyl group as a substituent in a molecule is called a
hydroxy group; an -oxy rather than an -oxyl ending is used.
Cyclic ethers contain ether functional groups as part of a ring system. Some examples of
such cyclic ethers, along with their common names, follow.
 Compounds Containing a Carbonyl Group

Aldehydes

Ketones
The IUPAC rules for naming aldehydes are as follows:

Rule 1: Select as the parent carbon chain the longest chain that includes the carbon atom of the
carbonyl group.

Rule 2: Name the parent chain by changing the -e ending of the corresponding alkane name to -al.

Rule 3: Number the parent chain by assigning the number 1 to the carbonyl carbon atom of the
aldehyde group. The number 1, however, does not become part of the name.

Rule 4: Determine the identity and location of any substituents, and append this information to the
front of the parent chain name.

Rule 5: When an aldehyde functional group is attached to a carbon ring, name the ring and add the
suffix -carbaldehyde.
The rules for IUPAC ketone nomenclature follow:

Rule 1: Select as the parent carbon chain the longest carbon chain that includes the carbon atom of the carbonyl group.

Rule 2: Name the parent chain by changing the -e ending of the corresponding alkane name to -one. This ending, -one, is
pronounced “own.”

Rule 3: Number the carbon chain such that the carbonyl carbon atom receives the lowest possible number. The position of
the carbonyl carbon atom is noted by placing a number immediately before the name of the parent chain.

Rule 4: Determine the identity and location of any substituents, and append this information to the front of the parent
chain name.

Rule 5: Cyclic ketones are named by assigning the number 1 to the carbon atom of the carbonyl group. Numbering then
proceeds in a clockwise or counterclockwise direction to give the next encountered substituent the lower number. The “1,”
designating the carbonyl carbon atom location, is omitted from the name.
2-Methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one
 Compounds Containing a Carbonyl Group

Carboxylic acids
IUPAC rules for naming monocarboxylic acid:

Rule 1: Select as the parent carbon chain the longest carbon chain that includes the carbon atom of the carboxyl
group.

Rule 2: Name the parent chain by changing the -e ending of the corresponding alkane to -oic acid.

Rule 3: Number the parent chain by assigning the number 1 to the carboxyl carbon atom, but omit this number
from the name.

Rule 4: Determine the identity and location of any substituents in the usual manner, and append this information
to the front of the parent chain name.

Rule 5: If the carbonyl group is bonded to a carbon ring, name the ring and add the words carboxylic acid. The
carbon bearing the carboxyl group is always carbon 1. Locate any other ring substituents in the usual manner.
 Compounds Containing a Carbonyl Group
Esters
 Compounds Containing a Carbonyl Group

Amides
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 often depend on alcohol class.

Combustion
As has been seen in the previous two chapters, 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.
Both methanol and ethanol, as well as alcohol-gasoline mixtures such as E10 and E85, are used as
automotive fuels.
Oxidation
Formal use of the oxidation number rules with organic compounds is usually cumbersome because of the
many carbon and hydrogen atoms present; often, fractional oxidation numbers for carbon result. A better
approach for organic redox reactions is to use the following set of operational rules instead of oxidation
numbers.

1. An organic oxidation is an oxidation that increases the number of C-O bonds and/or decreases the number
of C-H bonds.

2. An organic reduction is a reduction that decreases the number of C-O bonds and/or increases the number
of C-H bonds.

Primary and secondary alcohols, but not tertiary alcohols, readily undergo oxidation in the presence of mild
oxidizing agents to produce compounds that contain a carbon–oxygen double bond (aldehydes, ketones, and
carboxylic acids).
 (a primary alcohol)

No reaction

Tert-butyl alcohol
(a tertiary alcohol)
 Physical Properties of Alcohols
Polarity

Alcohol molecules have both polar and nonpolar character. The hydroxyl groups
present are polar, and the alkyl (R) group present is nonpolar
Boiling point

Small monohydroxy alcohols are soluble in water in all proportions. As carbon-chain length
increases beyond three carbons, solubility in water rapidly decreases because of the
increasingly nonpolar character of the alcohol.

Alcohols with two -OH groups present are more soluble in water than their counterparts with
only one -OH group.

Increased hydrogen bonding is responsible for this. Diols containing as many as seven carbon
atoms show appreciable solubility in water.
A comparison of the properties of alcohols with their alkane counterparts shows that

1. Alcohols have higher boiling points than alkanes of similar molecular mass.

2. Alcohols have much higher solubility in water than alkanes of similar molecular mass.

The differences in physical properties between alcohols and alkanes are related to
hydrogen bonding.

Because of their hydroxyl group(s), alcohols can participate in hydrogen bonding,

whereas alkanes cannot. Hydrogen bonding between alcohol molecules is similar to that
which occurs between water molecules.
The boiling points of ethers are similar to those of alkanes of comparable molecular mass
and are much lower than those of alcohols of comparable molecular mass. Ether molecules,
like alkanes, cannot hydrogen-bond to one another. Ether oxygen atoms have no hydrogen
atom attached directly to them.
Ethers have water solubilities similar to those of alcohols
of the same molecular mass.
For example, diethyl ether and butyl alcohol have the same
solubility in water.
Because ethers can also hydrogen-bond to alcohols, alcohols
and ethers tend to be mutually soluble.

Nonpolar substances tend to be more soluble in ethers

than in alcohols because ethers have no hydrogen-bonding
network that has to be broken up for solubility to occur.
Methyl Alcohol (Methanol)

Specially designed internal combustion engines can operate

using methyl alcohol as a fuel. For forty years, from 1965 to
2005, race cars at the Indianapolis Speedway were fueled with
methyl alcohol. A major reason for the switch from gasoline to
methyl alcohol relates to fires accompanying crashes. Methyl
alcohol fires are easier to put out than gasoline fires because
water mixes with and dilutes methyl alcohol.
Ethyl Alcohol Content (Volume Percent)
of Common Alcoholic Beverages, Household
Products, and Over-the-Counter Drugs
 The ethylene glycol and propylene glycol used
in antifreeze formulations are colorless and
odorless; the color and odor of antifreezes
come from additives for rust protection and the
like.

Also used as starting material for the manufacture of

polyester fibers
 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 and northern 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. It is used in candies and icings as
a retardant for preventing sugar crystallization.
Menthol is a naturally occurring terpene alcohol with a pleasant, minty odor. Its
IUPAC name is 2-isopropyl-5-methylcyclohexanol.

In the pure state, menthol is a white crystalline solid with a melting point of
41°C to 43°C. Menthol occurs naturally in peppermint oil. As is the case with
many natural products, the demand for menthol exceeds its supply from natural
sources. Methods now exist for the synthetic production of menthol.

Menthol’s mode of action is opposite that of capsaicin, the natural product

responsible for the “spiciness” of hot peppers. Capsaicin stimulates heat sensors
without causing an actual change in body temperature.

- Throat sprays and lozenges

- Cough drops and cigarettes
- Pre-electric shave preparations and aftershave lotions often contain menthol
- Many dermatologic preparations contain menthol as an anti-pruritic.
- Chest-rub preparations
- Mint fl avoring agents used in chewing gum and candies contain menthol as an
ingredient.
- Several toothpastes and mouthwashes also contain menthol as a flavoring
agent.
Physical Properties of Aldehydes and Ketones

Boiling points

The boiling points of aldehydes and ketones are intermediate between those of
alcohols and alkanes of similar molecular mass. Aldehydes and ketones have higher
boiling points than alkanes because of dipole–dipole attractions between
molecules.

Aldehydes and ketones have lower boiling points than the corresponding alcohols
because no hydrogen bonding occurs as it does with alcohols. Dipole–dipole
attractions are weaker forces than hydrogen bonds.
Solubility

Aldehydes and ketones having fewer than six carbon atoms are soluble in both organic
solvents and water. When six or more carbon atoms are present, such compounds are
soluble in organic solvents but not in water.

The water solubility of the smaller aldehydes and ketones results from water being able to
hydrogen bond to the lone pairs of electrons on the carbonyl oxygen atom.
Water Solubility (g/100 g H2O) for Various Aldehydes and Ketones
Oxidation of Aldehydes and Ketones

Aldehydes readily undergo oxidation to carboxylic acids, and ketones are resistant
to oxidation.
Several tests, based on the ease with which aldehydes are oxidized, have been
developed for distinguishing between aldehydes and ketones, for detecting the presence
of aldehyde groups in sugars (carbohydrates), and for measuring the amounts of sugars
present in a solution.

The most widely used of these tests are the Tollens test and Benedict’s test.
The Tollens test, also called the silver mirror test, involves a solution that contains silver
nitrate (AgNO3) and ammonia (NH3) in water.
Benedict’s test is similar to the Tollens test in that a metal ion is the oxidizing agent. With
this test, Cu2+ ion is reduced to Cu1+ ion, which precipitates from solution as Cu2O.
 Reduction of Aldehydes and Ketones

Aldehydes and ketones are easily reduced by hydrogen gas (H2), in the presence of a
catalyst (Ni, Pt, or Cu), to form alcohols. The reduction of aldehydes produces primary
alcohols, and the reduction of ketones yields secondary alcohols.
Formaldehyde is manufactured on a large scale by the oxidation of methanol. At room
temperature and pressure, formaldehyde is an irritating gas. Bubbling this gas through
water produces formalin, an aqueous solution containing 37% formaldehyde by mass
or 40% by volume. Formalin is used for preserving biological specimens.

Acetone, a colorless, volatile liquid with a pleasant, mildly “sweet” odor. Acetone is
an excellent solvent because it is miscible with both water and nonpolar solvents. The
presence of acetone in urine is a sign of diabetes. In severe diabetes, the odor of
acetone can be detected on the person’s breath.
Aldehydes and ketones occur widely in nature. Naturally occurring compounds of these
types, with higher molecular masses, usually have pleasant odors and flavors and are often
used for these properties in consumer products (perfumes, air fresheners, and the like).
Many important steroid hormones are ketones, including testosterone, the hormone that
controls the development of male sex characteristics; progesterone, the hormone secreted
at the time of ovulation in females; and cortisone, a hormone from the adrenal glands.
Synthetically produced cortisone is used as an anti-inflammatory medication.
Many commercial sunscreen formulations have ketones as their active ingredients.
Particularly common ingredients are aromatic ketones in which two non-fused benzene rings
are present. Examples of such ingredients are avobenzone, oxybenzone, and dioxybenzone.

Ketones of this type absorb ultraviolet (UV) light, which

enables sunbathers to control UV radiation dosage and
thus avoid sunburn (caused by too much UV radiation)
and yet develop a suntan (caused by a small amount of
UV radiation). Many people believe that a suntan is
desirable. Studies show, however, that sunbathing as well
as suntans, especially when sunburn results, ages the skin
prematurely and increases the risk of skin cancer.