Alcohols, phenols &

ethers
 Alcohols
 Alcohol : hydrocarbon derivative in which a
hydroxyl group (-OH) is attached to a
saturated carbon atom.
 General formula : R-OH

- C- OH alcohol functional group

 Alcohols have higher boiling points than

alkanes with similar molecular mass.
 Alcohols are more soluble in water than
alkanes.
 Alcohols
Alcohols are classified
 By the number of alkyl groups attached to the carbon bonded to the
hydroxyl.
 As primary (1°), secondary (2°), or tertiary (3°).

Primary (1º) Secondary (2º) Tertiary (3º)

1 group 2 groups 3 groups
H CH3 CH3
| | |
CH3—C—OH CH3— C—OH CH3—C—OH
| | |
H H CH3
 Nomenclature of Alcohols

3-ethyl-5-methylcyclohexanol

1.Select the longest continuous chain to which the hydroxyl group is directly attached.
2.Add the suffix -ol.
3.Number the longest continuous carbon chain so as to give the carbon atom bearing the hydroxyl group the
lower number.
4.Indicate the position of the hydroxyl group
5.Indicate the position of another substituent
 Nomenclature of Alcohols with More
Than One Hydroxyl Group

• An alcohol in which two hydroxyl groups are present, is named as diol.

• Alcohol containing three hydroxyl groups is named triol.
 Isomerism for Alcohols
 Constitutional isomerism is possible for alcohols containing 3 or more
carbon atoms.
 Both skeletal and positional isomers are possible.
 Physical Properties of Alcohols

 Alcohol molecules have both polar and nonpolar character.

 (a) The polar hydroxyl functional group dominates the physical properties of methanol.
 (b) Conversely, the nonpolar portion of 1- octanol dominates its physical properties.
Physical Properties of Alcohols
 Boiling point of alcohols increases as the
length of the carbon chain increases due to
increasing London forces.
 Boiling point of alcohol with more than one
hydroxyl group have higher boiling points
than their monohydroxy counterparts due
to increasing hydrogen bonding between
alcohol molecules.
 Solubility of alcohol in water is due to
hydrogen bonding and solubility decreases
with increasing length of carbon chain.

 Alcohols have higher boiling point and

more soluble in water than alkanes of
similar molecular mass.
 Preparation of Alcohols
1) Hydration of alkenes
2) Addition of H2 to carbonyl functional groups (aldehydes and ketones).

 Aldehydes undergo reduction to produce primary alcohols.

O OH

R- C-H + 2[H] R- C -H

H
 Ketones undergo reduction to produce secondary alcohol.
O OH

R- C-R’ + 2[H] R- C - R’
H
 Chemical Reactions of Alcohols

1) Combustion

Ethanol burns to give carbon dioxide and water

 Chemical Reactions of Alcohols

2) Intramolecular Alcohol Dehydration

Intramolecular dehydration reaction is an example of an elimination reaction (reaction in

which two groups or two atoms on neighbouring carbon atoms are removed from a
molecule leaving a multiple bond between the carbon atoms).
 Chemical Reactions of Alcohols
2) Intramolecular Alcohol Dehydration

 With molecules like butan-2-ol, dehydration can produce more than one alkene.

 The dominant product can be predicted using Zaitsev’s rule (major product is the alkene that has the
greatest number of alkyl groups attached to the carbon atoms of the double bond.
 Chemical Reactions of Alcohols
3) Intermolecular Alcohol Dehydration

 At a lower temperature (140°C), an intermolecular alcohol dehydration process can occur to produce
an ether, R-O-R.

 This is an example of condensation reaction (two molecules combine to form a larger one while
liberating a small molecule, usually water).
 Chemical Reactions of Alcohols
4) Oxidation
 It is the type of reaction where oxygen is added or
hydrogen is removed from an organic compound.

Potassium dichromate, K2Cr2O7 ,

potassium permanganate, KMnO4 and
chromic acid (H2CrO4) can be used as oxidising agent.
 Chemical Reactions of Alcohols
Oxidation
a) Primary alcohol

First stage:

Second stage:
 Chemical Reactions of Alcohols
Oxidation
b) Secondary alcohol
 Chemical Reactions of Alcohols

5) Halogenation

 Alcohol can also react with PBr3 to give similar products and heating is
required.
 PHENOL
 Phenol is a compound which has a OH attached to a carbon atom which is a
part of a benzene ring. General formula: Ar – OH.
 Ar represents aryl group (aromatic carbon ring system from which one
hydrogen atom has been removed)
OH

 slightly soluble in water

 phenols are weak acids in solution.
 Phenols cannot be oxidized by mild oxidizing agent but can be oxidized by
stronger oxidizing agent.
 Acidity of Phenols
 Phenol are slightly acidic because a hydrogen ion can break away from the -OH group and
transfer to a base.

 Phenol reacts with sodium hydroxide solution to give a colourless solution containing sodium
phenoxide.
 Ethers
 is an organic compound in which an oxygen atom is bonded to two carbon atoms by single
bonds.
 The carbon atoms that are attached to the O atom can be part of alkyl, cycloalkyl, or aryl
groups.

Common name: Dimethyl ether methyl phenyl ether

 Nomenclature for Ethers
IUPAC Name:
 Ethers are named as substituted hydrocarbons.
 The smaller hydrocarbon attachment and the oxygen atom are called an alkoxy group, and this
group is considered a substituent on the larger hydrocarbon group.
 Alkoxy group: is an – OR group, an alkyl (or aryl) group attached to an oxygen atom.

Anisole (aromatic ether)

 Isomerism for Ethers
Functional Group Isomerism
 Functional group isomers are constitutional isomers that contain
different functional groups.
 Example: C2H6O

Ethanol Methoxy methane

 Physical and Chemical properties of Ethers

 Boiling points of ethers are similar to those of alkanes of comparable molecular mass and
much lower than those of alcohols of comparable molecular mass.
 Ethers are soluble in water.
 Nonpolar substances are more soluble in ether than alcohol because ethers have no-hydrogen-
bonding network that has to broken up for solubility to occur.

Chemical properties:
 Ethers are flammable
 Ether reacts slowly with oxygen from the air to form unstable hydroperoxides and peroxides.
 Ethers are unreactive towards acids, bases and oxidizing agents.
 Cyclic ethers

 Cyclic ethers are compounds in which the ether functional group is part of a ring
system.
 Cyclic ethers are heterocyclic organic compounds (cyclic organic compounds in which
one or more of the carbon atoms in the ring have been replaced with atoms of
other elements)
 Sulfur Analogs of Alcohols

 Thiol: the sulfur analogs of alcohols contain – SH (sulfhydryl group) functional

groups instead of – OH functional groups.

Have low boiling points and a strong disagreeable odor.

 Properties of Thiols

 Thiols are easily oxidized to form disulfides.

 The oxidation of thiol has biological importance in the area of protein

chemistry.
 Interaction between –SH groups in cysteine molecules forms disulfide bridge
in protein molecules.
 Sulfur Analogs of Ethers
 Thioether : is an organic compound in which a sulfur atom is bonded to two carbon atoms by single
bonds.

 Thioethers are sometimes called sulfides.

IUPAC Name: methylthiomethane

Dimethyl sulfide

 Thiols are more reactive than alcohols and thioethers are more reactive than ethers.
 Thiols and thioethers are functional group isomers.