Alcohols, Phenols and Ethers

Alcohols and Phenols: Classification and Nomenclature

Alcohols have one or more hydroxyl groups attached to a carbon atom.

Phenols have one or more hydroxyl groups attached to a benzene ring.

Alcohols and phenols can be classified as primary, secondary or tertiary.

Some alcohols can be described as allylic, benzylic or vinylic alcohols.

In IUPAC nomenclature, the alcohol name is derived from the alkane name of

the longest continuous carbon chain.

IUPAC nomenclature of alcohols uses the “-ol” ending.

Phenol derivatives can be named as substituted phenols, but many have common
names.

The dihydroxyl benzene derivatives are actually better known by their common
names! Benzene-1, 2-diol is known as catechol or pyrocatechol. Benzene-1, 3-diol is
commonly referred to as resorcinol. Hydroquinone, or just quinol, is the common
name of benzene-1, 4-diol.

Ethers: Classification and Nomenclature

Ethers contain a bridging oxygen that links two carbon containing groups.
Simple, or symmetrical, ethers have two identical carbon groups on either side of the
oxygen.

Mixed, or unsymmetrical, ethers have different carbon groups on either side of the
oxygen.

Common names of ethers give the names of the carbon chains in alphabetical order.

In the IUPAC system, ethers are named alkoxyalkanes.

The larger group is considered to be the parent hydrocarbon. A number gives the
location of the alkoxy substitutent.

Structure of Functional Groups and Preparation of Alcohols and

Phenols

The hydroxyl group and the ether linkage in alcohols have an sp3 hybridised oxygen
and nearly tetrahedral geometry.

Acid-catalysed hydration of alkenes produces alcohols that follow Markovnikov’s

rule, but hydroboration-oxidation of alkenes gives anti- Markovnikov hydration.

Alcohols may be produced by the catalytic reduction of aldehyes and ketones,

reduction of carboxylic acids, or catalytic hydrogenation of esters.

Grignard reagents can be used to prepare a wide variety of alcohols from aldehydes
and ketones.

Phenols can e prepared from haloarenes, benzene-sulphonic acid, diazonium salts or

cumene.
Alcohols and Phenols: Physical Properties

The hydroxyl group chiefly determines the physical properties of alcohols and
phenols. The nature of the alkyl or aryl group does modify these properties to some
extent.

The boiling points of alcohols and phenols increases as the carbon chain increase in
length, but decrease as the chains become more branched.

Alcohols and phenols have higher boiling points than other organic molecules.

Alcohols and phenols are water-soluble.

Alcohols and Phenols: Chemical Reactions

Alcohols can act as both nucleophiles and electrophiles.

Alcohols and phenols react with active metals to form alkoxides or
phenoxides, while phenols can react with aqueous sodium hydroxide to
form phenoxides.
Alcohols and phenols are weakly acidic. Phenols are stronger acids than
alcohols.
Alcohols and phenols can react with carboxylic acids, acid chlorides and
carboxylic acid anhydrides to form esters.
Alcohols react with hydrogen halides to form alkyl halides, and with
phosphorus tribromide to form alkyl bromides.
Acid-catalysed dehydration of tertiary alcohols produces alkenes.
Primary and secondary alcohols can be oxidised to a variety of carbonyl-
containing compounds, depending on the oxidising agent chosen.
Passing vapours of primary or secondary alcohols over heated copper
forms aldehydes or ketones, ut tertiary alcohols under these conditions
form alkenes.

Specific Reactions of Phenols and Commercially Important Alcohols

Nitrophenols can be produced by reacting phenol with nitric acid.

The reaction of phenol with bromine gives different products, depending
on the solvent used.
Kolbe’s synthesis is used to prepare ortho-hydroxylbenzoic acid from
phenol.
The Reimer-Tiemann reaction converts phenol into salicylaldehyde.
Heating phenol vapours with zinc dust produces benzene.
Phenol can be oxidised to form quinones.
Methanol is prepared commercially by the catalytic hydrogenation of
carbon monoxide.
Ethanol can be prepared by the fermentation of sugars or by the hydration
of ethene.
Ethers: Preparation and Physical Properties

Dehydration of primary alcohols in the presence of an acid catalyst gives

ethers.
The preparation of ethers by the dehydration of primary alcohols occurs by
an SN2 mechanism.
The Williamson synthesis is an important method for preparing ethers. It
can be used in the laboratory to produce either symmetrical or
unsymmetrical ethers.
The Williamson synthesis works best with methyl or primary alkyl halides.
The alkoxide can be primary, secondary or tertiary in nature.
The boiling points of ethers are similar to the boiling points of alkanes
with comparable molecular masses.

Ethers: Reactions

Ethers can undergo acid-catalysed cleavage to form two molecules of alkyl

halides and one of water.
Acid-catalysed cleavage of alkyl aryl ethers breaks the alkyl-oxygen bond
to form phenol and an alkyl halide.
The alkoxy group is activating towards electrophilic substitution, and is
ortho, para directing.
Halogenation occurs by reacting the alkyl aryl ether with bromine in acetic
acid.
Alkyl aryl ethers can undergo Friedel-Crafts alkylation and acylation in the
presence of anhydrous aluminium chloride.