C 2730 LECTURE NOTES

ALCOHOLS AND ETHERS

So far we have been focusing on organic compounds whose structures are made up of carbon and
hydrogen atoms only (hydrocarbons). In the previous chapter, you were introduced to halogen-
containing derivatives of these compounds (alkyl halides or haloalkanes). At this stage you will be
introduced to organic molecules that contain, in addition to carbon and hydrogen, oxygen atom/s as
well. Alcohols, ethers, phenols and carbonyl compounds are examples of such compounds.

Alcohols are organic compounds that contain one or more hydroxyl (-OH) groups in their structures.
They are sometimes defined as derivatives (compounds derived from) of water (H 2O) in which one of the
hydrogen atoms of water has been substituted with an alkyl group (R) to form a new compound ROH.
The term alcohol is generally used to refer to compounds in which the hydroxyl group is attached to an
sp3 hybridized carbon. However, enols (OH is attached to as sp 2 carbon) and phenols (OH is attached to a
phenyl/benzyl group) are sometimes classified under this group.

Classification

Alcohols are classified as primary (1°), secondary (2°) or tertiary (3°) according to the number of alkyl
groups bonded to the hydroxyl-bearing carbon atom. Consider the following examples;

Primary alcohols

CH3OH

CH3CH2CH2CH2CH2CH2OH

Secondary alcohols

Tertiary alcohols

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Uses

1. Alcohols are used as organic solvents (eg methanol, ethanol, propanol)

2. Some alcohols are used as automobile fuel (ethanol)

3. They are also used to make disinfectants and sanitizers

4. Ethanol is the primary ingredient in alcoholic beverages

5. Alcohols can also be used in the preparation of other organic compounds

Properties

Toxicity

Although alcohols are domestically and industrially important, care must be taken while handling these
chemicals. For example, methanol is toxic to humans, causing blindness in small doses, and leads to
death if swallowed in large amounts. Ethylene glycol (1,2-ethanediol) and isopropyl alcohol (2-propanol)
are other alcohols that should not be drunk due to various toxic effects, mostly due to toxic metabolic
breakdown products.

Boiling Points

Alcohols have much higher boiling points than hydrocarbons and alkyl halides of similar molecular
weight. This is because of hydrogen-bonding in which a positively-polarized –OH hydrogen atom from
one molecule is attracted to a negatively-polarized oxygen atom of another molecule, resulting in a
weak force that holds molecules together. See illustration below;

δ+ δ+ δ- δ+ δ-
δ-
δ-
δ+ δ+

NB: Bonds denoted with broken lines (----) are hydrogen bonds.

In alcohols and water, both Vander Waals forces of attraction and hydrogen bonds must be broken for
boiling to occur. A lot more energy is required to achieve that, hence the high boiling points. This is not
the case in hydrocarbons and other organic compounds whose molecules are held together by the weak
Vander Waals forces only and lack hydrogen bonds.

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Amphoteric nature

Just like water, alcohols are both weakly basic and weakly acidic. As weak bases, they are reversibly
protonated by strong acids to yield oxonium ions, ROH 2+. eg,

As weak acids, they dissociate slightly in dilute aqueous solution by donating a proton to water to form
H3O+ and alkoxide ion, RO-. eg

Nomenclature (Naming)

The nomenclature of alcohols employs the same principles and guidelines that have already been laid
down in the previous chapters. Simple alcohols are named by the IUPAC system as derivatives of the
parent alkanes, by using the suffix –ol. Examples,

Some simple and widely occurring alcohols have common names that are accepted by the IUPAC. For
example,

HOCH2CH2OH Ethylene glycol (1,2-ethanediol)

HOCH2CH(OH)CH2OH Glycerol (1,2,3-propanetriol)

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H2C=CHCH2OH Allyl alcohol (2-propen-1-ol)

tert-butyl alcohol (2-methyl-2-propanol)

Benzyl alcohol (phenylmethanol)

NB: Common names are written first while the IUPAC names are in brackets

Preparation of Alcohols

Industrial preparation

Fermentation is one of the oldest methods for the preparation of alcohol, particularly ethanol. It is
usually done by using yeast to act on carbohydrates to produce ethanol and carbon dioxide. Sugar cane,
rice malt, barley, fruits etc are usually used as raw materials in this process.

Laboratory scale preparations

1. From alkenes by hydration (see reactions of alkenes)

Water adds to alkenes to form alcohols in a process called hydration.

a) Hydration under acid conditions

b) Oxymercuration-demercuration

c) Hydration via hydroboration

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Note that the first two hydration techniques yield Markovnikov’s products while the last one generates
Anti-Markovnikov’s products.

2. From alkyl halides by substitution reactions (see reactions of alkyl halides)

R-X + NaOH R-OH + NaX

CH3CH2CH2CH2CH2Br + NaOH CH3CH2CH2CH2CH2OH + NaBr

3. From the reduction of carbonyl compounds (aldehydes, ketones, carboxylic acids, esters…etc)

Carbonyl compounds, which are characterized by the presence of a carbonyl group (O=C-) can be
reduced to produce alcohols. In this reduction reaction, a pi bond between carbon and oxygen atoms is
broken, followed by addition of two hydrogen atoms (one to C atom and the other to O atom). Several
reducing agents are known, and the choice of a reagent depends on the nature and the type of the
carbonyl starting material. Any carbonyl compound can be reduced, including aldehydes, ketones,
carboxylic acids and esters. Sodium borohydride (NaBH4) and lithium aluminium hydride (LiAlH4) are by
far the commonest reducing agents found in our laboratories. Although milder, NaBH 4 is however
usually chosen for its safety and ease of handling.

Reduction of aldehydes and ketones

Aldehydes are easily reduced to give primary alcohols, and ketones are reduced to give secondary
alcohols.

Consider;

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Reduction of carboxylic acids and esters

The reduction of carboxylic acids yields primary alcohols. A more powerful reducing agent (LiAlH 4) is
used in this case.

4. From hydrolysis of esters

An ester is hydrolysed, either by aqueous base or acid, to yield a carboxylic acid plus an alcohol.

5. From ethers by hydrolysis

When ethers are treated with strong acid in the presence of a nucleophile, they can be cleaved to give
alcohols and other compounds depending on the type of a nucleophile used. When water is the
nucleophile, two alcohol molecules are produced upon hydrolysis.

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6. By reaction of carbonyl compounds with Grignard reagents

Safe for methanol, all aldehydes react with Grignard reagents to produce secondary alcohols while
ketones react to produce tertiary alcohols.

Esters react with Grignard reagents to yield tertiary alcohols in which two of the alkyl substituents
bonded to the hydroxyl-bearing carbon have come from the Grignard reagent. For example,

Reactions of Alcohols

1. Dehydration

Alcohols can be converted into alkenes by elimination reaction. In this reaction, water is removed from
the alcohol. The reaction can be carried out under acid or base conditions. (check the preparation of
alkenes from alcohols from your notes)

2. Oxidation (conversion of alcohols to carbonyl compounds)

Primary alcohols are oxidized into aldehydes while secondary alcohols are oxidized to ketones. Tertiary
alcohols are not oxidisable. Strong oxidizing agents convert a primary alcohol to a carboxylic acid state.
Several oxidizing agents such as KMnO4, Pyridinium chlorochromate (PCC), pyridinium dichromate (PDC),
Na2Cr2O7, AgNO3 and chromium salts and oxide are used.

Consider the following;

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Examples

3. Esterification (formation of esters)

Alcohols readily react with acid halides (acyl halides), acid anhydrides and carboxylic acids to produce
salts of carboxylic acids called ESTERS. This reaction is analogous to an inorganic reaction in which an
acid reacts with a base to produce salt plus water. The order of reactivity of alcohols toward these
reactants is acyl halides > acid anhydrides > carboxylic acids.

CH3COBr + CH3OH CH3COOCH3 + H2O

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Esterification reaction is used to synthesize important drugs such as aspirin. In this reaction, salicylic acid
is reacted with acetic anhydride in aqueous sodium hydroxide to produce the desired product.eg

4. Conversion into ethers

Alcohols are converted into ethers by formation of the corresponding alkoxide ion followed by reaction
with alkyl halide, a reaction known as the Williamson ether synthesis.

Mechanistically, the Williamson synthesis is an SN 2 reaction, and occurs by nucleophilic substitution of

5. Reaction with carbonyl compounds (formation of hemi-acetals and acetals)

Alcohols react with aldehydes and ketones in the presence of acid catalyst to form acetals (compounds
with two ether-like –OR groups bonded to the same carbon atom).

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ETHERS

Ethers are organic compounds that are similar to alcohols although they are characterized by an oxygen
atom bonded to two alkyl or aryl groups (R-O-R’, where R and R’ represent an alkyl or aryl group). Such
type of a bond is known as an ether bond. Most ethers like diethyl ether, 1,4-dioxane, glyme and
tetrahydrofuran (THF) are colourless liquids which are used as solvents in our laboratories. They are
generally unreactive (except for highly strained cyclic members).

The boiling points of ethers are higher than those of alkanes of similar molecular weight, but lower than
those of alcohols of comparable molecular weights.

Nomenclature

The IUPAC system for naming ethers treats them as alkanes that bear an alkoxy group; that is as
alkoxyalkanes. The smaller substituent is considered part of the alkoxy group, and the larger defines the
parent.

Examples

1. CH3OCH2CH3 METHOXYETHANE
2. CH3CH2OCH2CH3 ETHOXYETHANE
3. CH3OCH3 METHOXYMETHANE

Many ethers are however known by their common names which site the two alkyl groups (in
alphabetical order) followed by the term ether. For example, CH 3OCH2CH3 is known as ethyl methyl
ether, while CH3OCH3 is known as dimethyl ether.

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More examples

Name compound 4 by the IUPAC system….

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