Alcohols, Ethers, Phenols, Thiols
BONDING CHARACTERISTICS OF OXYGEN ATOMS IN ORGANIC COMPOUNDS
Alcohols
An alcohol is defined as an organic compound that features a hydroxyl group, designated as -OH,
covalently bonded to a saturated carbon atom. A saturated carbon atom is one that is bonded to four
other atoms, indicating the completeness of its tetravalence. The presence of the hydroxyl group is
what characterizes alcohols, marking them distinctly from other organic compounds.
Nomenclature for Alcohols
The International Union of Pure and Applied Chemistry (IUPAC) has established specific rules
for naming alcohols possessing a single hydroxyl group:
• Rule 1: Identify the longest carbon chain that contains the hydroxyl group. The name of this
chain can be derived from that of the corresponding alkane by removing the final -e and
adding the suffix -ol.
• Rule 2: Number the carbon chain starting from the end nearest to the -OH group. This
numbering serves to indicate the position of the hydroxyl group, with its priority established
over double and triple bonds as well as other substituents.
• Rule 3: Include names and positions of other substituents in the compound.
• Rule 4: In cases where the hydroxyl group is attached to a carbon in a ring structure, it is
assumed to be on carbon 1. Numbering then proceeds around the ring to ensure that the
subsequent substituents receive the lowest possible numbers. The designation of carbon 1
is typically omitted from the name.
Alcohols with More Than One Hydroxyl Group
Alcohols with multiple hydroxyl groups are known as polyhydroxy alcohols. Specifically, a compound
with two hydroxyl groups is categorized as a diol, while those with three hydroxyl groups are termed
triols. For the naming conventions of diols and triols, the final -e of the parent alkane name is retained
for phonetic clarity.
Commonly Encountered Alcohols
There are several notable alcohols frequently encountered in various contexts:
• Methyl Alcohol (Methanol): This simplest alcohol consists of one carbon atom and one
hydroxyl group. Methanol is a colorless liquid known for its effectiveness as a fuel for internal
combustion engines, as it is less challenging to extinguish than gasoline fires. It is also
recognized for its solvent capabilities in applications such as paints and varnishes but is toxic
if ingested.
• Ethyl Alcohol (Ethanol): Often simply referred to as alcohol, ethanol is the primary
component of alcoholic beverages. It possesses recreational and psychoactive properties,
undergoing metabolic oxidation in the body to acetaldehyde, which is associated with
hangover symptoms.
• Isopropyl Alcohol (Isopropanol): Commonly known as rubbing alcohol, this compound is a
70% isopropyl alcohol and 30% water solution that rapidly evaporates and cools upon
application to the skin. However, it has significantly higher toxicity than ethanol.
• Ethylene Glycol and Propylene Glycol: Both of these compounds are diols, with ethylene
glycol being notably toxic when ingested, while propylene glycol is generally safe and often
utilized as a solvent in pharmaceuticals.
• Glycerol (Glycerin): This triol is a sweet, viscous liquid naturally occurring in the body as a
fat metabolism product and is also added to various topical pharmaceuticals for moisture
retention.
Classification of Alcohols
Alcohols are classified based on the number of carbon atoms bonded to the carbon atom that
carries the hydroxyl group:
• Primary Alcohols (1°): The hydroxyl-bearing carbon atom bonds to only one other carbon
atom.
• Secondary Alcohols (2°): The hydroxyl group is bonded to two other carbon atoms.
• Tertiary Alcohols (3°): The hydroxyl is connected to three additional carbon atoms.
Chemical Reactions of Alcohols
Combustion
• Reaction: Alcohols readily undergo combustion when reacted with oxygen (O₂).
• Products: The products of combustion are carbon dioxide (CO₂) and water (H₂O), similar to
the combustion of hydrocarbons.
Intramolecular Alcohol Dehydration
• Definition: Intramolecular dehydration is a reaction where water (H₂O) is removed from a
single alcohol molecule.
• Conditions: This reaction typically occurs under high temperature and in the presence of a
catalyst such as sulfuric acid (H₂SO₄).
• Product: The result is the formation of an alkene (a double bond between carbon atoms).
Intermolecular Alcohol Dehydration
• Definition: Intermolecular dehydration is a condensation reaction where two alcohol
molecules combine.
• Product: This results in the formation of an ether and water.
Halogenation
• Reaction: Alcohols undergo halogenation, where a halogen atom (e.g., Cl, Br, I) substitutes
the hydroxyl group (-OH).
• Product: The product is an alkyl halide (R–X), where X is the halogen.
Structural Characteristics of Phenols
Phenols
• Definition: A phenol is an organic compound that contains a hydroxyl group (-OH) attached
to a carbon atom within an aromatic ring (aromatic alcohol). The general formula is Ar–OH.
Nomenclature for Phenols
• IUPAC Naming: The simplest member of the phenol family is named phenol. The numbering
of the ring starts at the position of the hydroxyl group to give it priority in naming.
Physical and Chemical Properties
• State: Phenols are generally low-melting solids or oily liquids at room temperature.
• Antiseptic Properties: Many phenols exhibit antiseptic properties.
• Solubility: Phenols are less soluble in water than alcohols due to the presence of the bulky
aromatic ring.
Alcohols vs. Phenols
• Flammability: Both alcohols and phenols are flammable, but they differ in their reactivity.
o Dehydration: Dehydration reactions are typical for alcohols, but not for phenols.
o Halogenation: Phenols undergo halogenation reactions (e.g., with chlorine or
bromine) more readily than alcohols.
Sulfur Analogs of Alcohols
Thiol Compounds
• Definition: Thiols are the sulfur analogs of alcohols, containing a sulfhydryl group (-SH) in
place of the hydroxyl group (-OH).
• Nomenclature: The nomenclature for thiols follows the same pattern as alcohols, except the
suffix -thiol replaces -ol (e.g., methanethiol).
Aldehydes and Ketones
Introduction
• Aldehydes: Contain a carbonyl group (C=O) bonded to a terminal carbon atom and a
hydrogen atom (–CHO).
• Ketones: Contain a carbonyl group bonded to two additional carbon atoms (–CO–).
Nomenclature
• Aldehydes: Named by replacing the final -e of the corresponding alkane name with -al (e.g.,
ethanal from ethane).
• Ketones: Named by replacing the final -e of the corresponding alkane name with -one (e.g.,
propanone from propane).
Physical Properties
• Boiling Points: Aldehydes and ketones have higher boiling points than hydrocarbons of
similar molecular weight due to the polarity of the carbonyl group.
• Hydrogen Bonding: While they are polar, aldehydes and ketones do not form strong hydrogen
bonds with each other, unlike alcohols.
Synthesis of Aldehydes and Ketones
• Methods for Aldehyde Synthesis:
o Oxidation of primary alcohols.
o Ozonolysis of alkenes.
o Reduction of carboxylic acid derivatives.
Carboxylic Acids, Esters, and Other Acid Derivatives
Carboxylic Acids
• Definition: Organic compounds containing a carboxyl group (-COOH), which is
characterized by a carbonyl group (C=O) bonded to a hydroxyl group (-OH).
• Properties: Carboxylic acids have high polarity and high boiling points due to their ability to
form hydrogen bonds and dimerize.
Nomenclature
• IUPAC Naming: The IUPAC name for monocarboxylic acids is derived by identifying the
longest carbon chain that includes the carboxyl group, replacing the -e ending of the alkane
name with -oic acid.
Preparation of Carboxylic Acids
• Methods: Carboxylic acids can be synthesized via:
o Oxidation of aldehydes.
o Hydrolysis of cyanohydrins and nitriles.
Acidity of Carboxylic Acids
• De-protonation: Carboxylic acids are acidic and can lose a proton (H+) in water, forming the
corresponding carboxylate anion.
Esters
• Definition: Esters are organic compounds formed by the reaction between a carboxylic acid
and an alcohol through a condensation reaction called esterification.
Nomenclature of Esters
• The nomenclature for esters involves:
o Naming the alcohol part first (with the suffix -yl).
o Naming the deprotonated carboxylic acid part (with the suffix -ate).
Physical Properties of Esters
• Boiling Points: Esters generally have lower boiling points than their parent carboxylic
acids due to the absence of the -OH group, which limits hydrogen bonding capabilities.
ACID ANHYDRIDES AND ACID HALIDES
INTRODUCTION
• Definition: Acid anhydrides are compounds formed by the removal of a water molecule from
two carboxylic acid molecules.
• Composition: They are considered derivatives of carboxylic acids, typically containing two
acyl groups (RCO-) linked by an oxygen atom.
• General Formula: RCO−O−COR, where the R groups can be identical or different.
STRUCTURE OF ACID ANHYDRIDE
• Meaning: The term "anhydride" signifies the absence of water.
• Molecular Structure: Contains two acid molecules, losing a water molecule in the process.
• Reformation: Addition of water to an anhydride regenerates two carboxylic acid molecules.
NOMENCLATURE OF ACID ANHYDRIDES
• Naming Convention: The term "acid" is replaced by "anhydride" in both common and IUPAC
names.
• Examples:
o Ethanoic acid → ethanoic anhydride
o Propanoic acid → propanoic anhydride
TYPES OF ACID ANHYDRIDES
• Symmetrical Anhydrides: Both acyl groups are the same (e.g., acetic anhydride,
(CH3CO)2O).
• Mixed Anhydrides: Different acyl groups (e.g., acetic formic anhydride), named by
alphabetizing the acid names and replacing "acid" with "anhydride."
PREPARATION OF ACID ANHYDRIDES
• Methods:
o Reacting an acid chloride with carboxylic acid to form an anhydride.
o Reacting an acid chloride with carboxylate salt.
o Heating carboxylic acids with zinc oxide.
o Heating dicarboxylic acids to yield cyclic anhydrides.
REACTIVITY OF ACID ANHYDRIDES
• Comparison with Acyl Chlorides:
o Ethanoic anhydride has a bulky ethanoate group attached to a carbonyl, making it
less reactive than ethanoyl chloride, which has a simple Cl atom attached.
REACTIONS OF ACID ANHYDRIDES
• Types of Reactions:
o Hydrolysis: Produce carboxylic acids, can occur in acidic or basic conditions,
leading to carboxylate salts in basic solutions.
o Alcoholysis: React with alcohol to produce esters and carboxylic acids, typically
requires heating but no catalyst.
o Ammonolysis: Forms amides upon reaction with ammonia, primary or secondary
amines.
o Friedel-Crafts Acylation: A method of introducing acyl groups into aromatic
compounds.
ALKYL HALIDES
• Definition: Organic molecules containing a halogen atom bonded to an sp3 hybridized
carbon atom.
• Classification: Alkyl halides are categorized as primary (1o), secondary (2o), or tertiary (3o),
based on the number of carbons attached to the carbon with the halogen atom.
• General Formula: R-X, where R is an alkyl group and X is a halogen (Cl, Br, F, I).
AMINES
• Definition: Organic compounds that contain nitrogen atoms bonded to carbon atoms.
• Classification: Amines are designated as primary, secondary, or tertiary based on the
number of carbon groups attached to nitrogen.
• Definition: A carboxylic acid derivative where the hydroxyl (-OH) group has been substituted
by an amino or substituted amino group.
• Classification:
o Primary amides: Two hydrogen atoms bonded to nitrogen.
o Secondary amides: One hydrogen and one carbon group bonded to nitrogen.
o Tertiary amides: No hydrogen bonded to nitrogen, two carbon groups attached.
PHYSICAL PROPERTIES
• Amines: Exhibit higher boiling points compared to alkanes due to hydrogen bonding. Lower
boiling than alcohols due to weaker N---H bonds. Soluble in water due to hydrogen bonding.
• Amides: Higher melting points from strong intermolecular hydrogen bonds. Solubility in
water for low molecular mass amides, as they can form hydrogen bonds with water.
