ALCOHOLS, ETHERS, AMINES AND NITRILES

ALCOHOLS

Alcohols are derivatives of hydrocarbons in which a hydroxyl group (OH) has replaced a hydrogen atom. They
have the general formula R-OH, where the R group can represent the alkyl, alkenyl, or alkynal groups. All
alcohols have one or more hydroxyl functional groups; the OH group in an alcohol molecule is attached to a
carbon atom by a covalent bond hence, they are covalent molecules. They can be named by both common
and IUPAC system. The name of an alcohol comes from the hydrocarbon from which it was derived. The final
“e” in the name of the hydrocarbon is replaced by –“ol”, and the carbon atom to which the “OH” group is
bonded is indicated by a number placed before the name.

 Types of Alcohols

There are three categories of alcohol namely: Primary, Secondary and Tertiary Alcohols. The hydroxyl group
is classified according to where an alkyl group carbon atom is bound to the hydroxyl group.

Primary Alcohol

Primary alcohols are alcohols in which the hydroxyl group is attached to terminal carbon atom. E.g.
CH3CH2OH. Ethanol

Secondary Alcohol

Secondary Alcohols are alcohols in which the carbon atom of the hydroxyl group is attached to two alkyl
groups, E.g. CH3CHOHCH3 propan-2-ol.

Tertiary Alcohol

These are alcohols in which the carbon atom to which hydroxyl group is attached is connected to three alkyl
groups. CH3C(OH)CH3CH3 2-methylpropan-2-ol. In addition, alcohols can further be classified based on
the number of hydroxyl groups present: monohydric alcohol, dihydric alcohol, trihydric alcohol and
polyhydric alcohol. Monohydric alcohols are alcohols that contain only one hydroxyl group, dihydric alcohols
contain two hydroxyl groups, trihydric contain three hydroxyl groups and polyhydric alcohols contain more
than three hydroxyl groups.

 PHYSICAL PROPERTIES OF ALCOHOLS

i. Alcohols are flammable and produce a blue flame

ii. Alcohols are acidic in nature

iii. Some alcohols do not produce flame while burning

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 iv. Alcohols are colourless

v. Alcohols have higher boiling point compared with other hydrocarbons

vi. Alcohols are soluble in water than other hydrocarbon due to polar hydroxyl bond

vii. Alcohols are liquid at room temperature

viii. Alcohols give a sweet smell with the exception of glycerol and a few lower alcohols

 REACTIONS OF ALCOHOL

i. Oxidation of Alcohols: this is a chemical reaction involving the conversion of hydroxyl group into
other functional groups such as: carboxylic acid, ketone and aldehyde. Primary alcohols are
oxidized into Aldehyde and Carboxylic acid, while secondary alcohols are oxidized to ketone
because carbon-to-hydrogen bonds are easily broken and tertiary alcohols cannot be oxidized
because C–C bonds are not easily broken in the molecule.

ii. Dehydration of Alcohols:

This chemical reaction involves the cleavage of a C-O bond and the loss of a proton from the beta
carbon. The formation of a chemical known as the carbo cation intermediate occurs during the
dehydration of secondary and tertiary alcohols.

iii. Esterification of Alcohols: this is a chemical reaction involving an alcohol and an acid to produce
an ester as the reaction product. For example, ethyl ethanoate is produced by gently heating a
mixture of ethanoic acid and ethanol in the presence of concentrated Sulphuric acid.

 General Methods of Preparation of Alcohols

i. Hydrolysis of Halides: this involves boiling of Alkyl halides with an aqueous solution of an
alkali hydroxide to give alcohol through nucleophilic substitution mechanism.

CH3-Cl + KOH → CH -OH + KCl

3

ii. Hydroformylation of Alkenes (Oxo reaction): this is a reaction involving lower molecular
weight olefins reacting with carbon monoxide and hydrogen in the presence of a catalyst to
produce Aldehyde. The Aldehyde is consequently hydrogenated to form an alcohol.

iii. Hydration of Alkenes: this is the classified into two; direct and indirect hydration. Direct
hydration is the addition of water to alkenes in the presence of a catalyst. The pi bond (=) is

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 broken, thus the -OH from water molecule is attached to the –C-H to form –COH bond while,
indirect hydration is the addition of sulphuric acid to alkene and then hydrolyse by the alkyl
hydrogen sulfate.

iv. Grignard Synthesis: Alcohols can be prepared by reacting Grignard reagents with carbonyl
compounds. Primary alcohols are produced by reacting methanal with Grignard reagent,
reaction of aldehyde other than methanal produces secondary alcohol and tertiary alcohol is
produced by Ketones reacting with Grignard reagent.

ETHERS

Ethers are organic compounds which contain oxygen bonded to two alkyl or aryl groups (R-O-R’, R-O-Ar, Ar-
O-Ar’). In the general formula for ethers, R—O—R, the hydrocarbon groups (R) may be the same or different.
They are named depending on the alkyl/aryl group bonded to Oxygen then ether. The two branches
connected to the oxygen atom are named separately and followed by ―ether. They can be classified into
symmetrical and unsymmetrical or asymmetrical. Symmetrical ethers are ethers which the Oxygen atom is
bonded to identical group of compounds. E.g. Diethylether CH3-CH2-O-CH2CH3, when the Oxygen atom in
ether is bonded to different group of atoms it is called asymmetrical ethers. e.g. Ethylpropylether CH3-CH2-
O-CH2 CH2-CH3.

 PHYSICAL PROPERTIES OF ETHERS

i. Ethers are soluble in water. Their solubility increases with increase in carbon atom.

ii. Ethers are colourless and volatile liquids, which are highly flammable.

iii. The boiling point of ethers is similar to alkanes but lower than that of alcohols

 REACTIONS OF ETHERS

i. Halogenation: the alkyl group of the ether is reacted with halogens (Cl, Br etc) in the absence
of sunlight to produce halogenated ether.

CH3-CH2-O-CH2CH3 Cl2 (dark) CH3-CHCl-O-CHClCH3

ii. Nitration: this is the reaction between aromatic ether and strong sulphuric acid and nitric acid.
E.g. formation of ortho and para anisole by reacting anisole with strong sulphuric acid and
nitric acid.

iii. Friedel-craft reaction: this is the chemical reaction between aromatic ether and alkyl or acyl
halide in the presence of lewis acid which act as catalyst. E.g. reaction between anisole and
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 methyl chloride in the presence of anhydrous aluminium chloride.

iv. Combustion: ethers are combustible when in contact with air hence, they form carbondioxide
and water.

C2H5OC2H5 + 6O2 4CO2 + 5H2O

 Preparation of Ethers

i. Preparation of ethers by Williamson Synthesis: this is the preparation of ether by reacting

alkyl halide with sodium alkoxide. E.g. reaction between ethylchloride and Sodium ethoxide to
produce diethylether and sodium chloride.

CH3CH2Cl + CH3CH2-O-Na CH3CH2- O- CH2CH3 + NaCl

ii. Dehydration of alcohol: ethers can be prepared by dehydrating alcohol in the presence of
protic acid (such as Nitric acid, Sulphuric acid and Hydrochloric acid) to produce alkenes and
ether under different condition.

H2SO4/443K CH2 = CH2

CH3CH2OH

H2SO4/413K C2H5OC2C5

AMINES

Amines
Amines are molecules that contain carbon-nitrogen bonds. The nitrogen atom in an amine has a lone pair of
electrons and three bonds to other atoms, either carbon or hydrogen. Amines are derivatives of ammonia in
which one or more hydrogen atom (s) have been replaced by alkyl or aryl(phenyl) group. They have the
general formular R3-xNHx. They can be classified as: Primary Amines RNH2, Secondary amine RR’NH and
Tertiary amine RR’R’’NH
 Primary amines: these are amines formed by replacing one hydrogen atom of ammonia by alkyl or aryl
group e.g. methylamine, ethylamine, propylamine, phenylamine (aniline)
 Secondary amines: are those formed by replacing two hydrogen atoms of ammonia by alkyl or aryl
group e.g. diethylamine, dipropylamine, diphenylamine, ethylmethylamine, methylpropylamine.
 Tertiary amines: these are formed by replacing all the three hydrogen atoms of ammonia by alkyl or
aryl group e.g. trimethylamine, triethylamine, tripropylamine, triphenylamine,
ethylmethylpropylamine.
Also, amines are grouped into two: Simple and Mixed. When all the alkyl or phenyl groups in secondary and

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tertiary amines are the same, they are called Simple amines. Examples are diethylamine, dipropylamine,
diphenylamine, trimethylamine, triethylamine, tripropylamine, triphenylamine and are called mixed amines
when all the alkyl or phenyl groups in secondary and tertiary amines are not the same. Examples are
ethylmethylamine, methylpropylamine, ethylmethylpropylamine.
IUPAC NOMENCLATURE OF AMINES
Amines are amino group containing –NH2. They are named as alkylamine for example Primary amines are
named by naming the alkyl group bonded to the amino group (–NH2) and the suffix “-amine” is added.
Examples are: Methylamine (CH3–NH2), Butylamine (C4H7–NH2) e.t.c.
Secondary and tertiary amines are named by arranging the alkyl groups alphabetically as in
Ethylmethylamine (C2H5NHCH3), Ethylmethylamine (CH3NH C2H5), Methylphenylamine (CH3NH(C6H5) and
when two or more identical alkyl groups are present, the prefixes “ di, tri” are used e.g. Diethylamine
(C2H5NHC2H5).
PHYSICAL PROPERTIES OF AMINES
i. Lower alkyl amines have notorious fishy ammonia smells.
ii. Lower aliphatic amines (methylamine and ethylamine) are highly soluble in water while the solubility
of higher amines decreases with increase in molecular weight.
iii. Lower aliphatic amines (methylamine and ethylamine) are gases at room temperature and higher
members are liquids, then solids.
iv. Amines have higher boiling points than alkanes of similar molecular weight but lower boiling points
than alcohol due to their C-N bond being more polar than C-C bond but less polar than C-OH bond.
Note: Tertiary amines have lower boiling points than Primary and Secondary amines because Primary and
secondary amines are hydrogen bond donors and acceptors while no hydrogen atoms is bonded to the
nitrogen atom in tertiary amine.
CHEMICAL PROPERTIES OF AMINES
i. Reaction of Amines with Nitrous acid
 Primary aliphatic amines react with nitrous acid to yield gaseous nitrogen. For example, the reaction
of ethylamine with nitrous acid involves the replacement of –NH2 by –OH and nitrogen gas is evolved.
C2H5NH2 + HNO2 C2H5OH + N2 + H2O
 Secondary amines (both aliphatic and aromatic) react with nitrous acid to give nitroso compounds.
(C2H5)2NH + HNO2 (C2H5)2N-N=O + H2O
 Tertiary amines react with nitrous acid to give solutions containing substituted ammonium nitrites
(CH3)3N + HNO2 (CH3)3 + NHNO2-
ii. Alkylation of Amine
Alkylation of amine is the conversion of primary amines to secondary amines and probably to tertiary
amine by reacting alkylhalides (such as: RI, RBr, RCl etc) and amine.
NOTE: the order of reactivity of alkylhalide RI is greater than RBr greater than RCl.

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 iii. Basic Character of Amine
All primary amines are bases. Reaction of Amine with acids form well defined crystalline salts.
RNH2 + HA RN+H3 + A-
For example; C2H5NH2 + HCl C2H5N + H3 + Cl-
lower alkylamines are only a little stronger than ammonia as bases and they are highly soluble in water.
Ethylamine and other volatile amines show the characteristics “white cloud” with hydrogen chloride (or any
other acid in the vapour state as ammonia).
iv. Acylation of Amines
This is a reaction by which amines are converted into amides. It involves the replacement of an hydrogen
atom of the -NH2 group by an acyl group (R’CO). Generally, acylation can be carried out by four characteristic
reagent types via; Acylchloride R’COCl, Acid anhydride (R’C (O)2 O, Carboxylic acid R’COOH and carboxylate
ester R’COOC2H5
For example: acetylation of ethylamine, the possible reactions are as follows:
a) C2H5NH2 + CH3COCl C2H5NHCOCH3 + HCl
b) C2H5NH2 + (CH3CO)2O C2H5NHCOCH3 + CH3COOH
c) C2H5NH2 + CH3CO2H C2H5NHCOCH3 + H2O
d) C2H5NH2 + CH3CO2C2H5 C2H5NHCOCH3 + C2H5OH

Preparation of Amines
i. Ammonolysis of simple alcohol: this is the reaction of Alcohol with Ammonia. For example,
Reaction of Ethanol with ammonia using aluminium oxide/silica gel at 3600C produces mixture of primary,
secondary and tertiary amines.
C2H5OH + HNH2 Al2O3 /Silica gel at 3600C C2H5NH2 + H2O
C2H5OH + C2H5NH2 Al2O3 /Silica gel at 3600C (C2H5)2NH + H2O
0
C2H5OH + (C2H5)2NH Al2O3 /Silica gel at 360 C (C2H5)3N + H2O
ii. Ammonolysis of Alkylhalides: This is the reaction between alkylhalides and ammonia. All classes
of amines can be prepared by this method:
C2H5Cl + NH3 C2H5NH2 + HCl (primary amine)
C2H5Cl + C2H5NH2 (C2H5)2NH + HCl (secondary amine) e.t.c.
iii. Reduction Methods
Reduction of primary amines can be achieved by the following: Nitro compounds
(RNO2); Cyanides/Nitrile (RCN); Amide (R-CONH2), Oximes (RR’C=NOH).
a) Reduction of Nitro compound: Nitro compounds are reduced into primary amine in the presence of
hydrogen as reducing agent and Raney Nickel catalyst.
C2H5NO2 + 3H2 Ni C2H5NH2 + 2H2O
b) Reduction of Nitrile: Primary amines are produced by the reduction of Nitriles in the presence of

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 Hydrogen.
R-C N [H] R-CH2NH2
c) Reduction of Amide: amides are reduced into primary amine in the presence of
lithiumaluminiumhydride as catalyst.
R-CONH2 LiAlH4 R-CH2NH2 + H2O
NITRILES

Nitriles are a class of organic compounds containing the functional group C N. The simplest nitriles are:
ethanenitrile (CH3-C N), propanenitrile (CH3CH2-C N), butanenitrile (CH3CH2 CH2-C N).

Physical properties of Nitriles

i. They are highly soluble in water, and their solubility decreases with increases in chain length.

ii. They show high polarity and electronegativity.

iii. Their boiling point ranges between 82-118 °C.

iv. They exhibit strong dipole-dipole movements and the Van der Waals forces of dispersion between
molecules.

REACTION OF NITRILES

i. Hydrolysis- nitriles can be hydrolysed in the presence of an acid or a base to produce

carboxamides and carboxylic acids.

ii. Alkylation- The alkylation of nitrile compounds leads to the formation of nitrile anions.

Reduction- Nitriles are reduced to primary and tertiary amines by treating them with lithium aluminium
hydride. The reduction process occurs in the presence of some catalysts.

The other reactions are nucleophilic addition reactions, Friedel–Crafts acylation, etc.

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