INTRODUCTION TO ORGANIC CHEMISTRY

In the beginning of modern science, compounds were grouped into organic and inorganic.
Organic compounds were defined as compounds that were obtained from living organisms only
while inorganic compounds were those that came from non-living organisms. Scientists believed
that vital force which was needed in the production of the organic compounds could only be
found in the living organisms. Therefore the idea was that organic compounds could not be
synthesized in flasks in the laboratory.
The idea gradually went into extinction when Wöhler in 1828 obtained an organic compound
(Urea) by evaporating an aqueous solution containing an inorganic compound (ammonium
cyanate).

O
heat
NH4+NCO C
H 2N NH2
ammonium cyanate
urea

Carbon was found to be central to organic compounds and organic chemistry is defined as the
chemistry of the compounds of carbon except carbon (II) oxide, carbon (IV) oxide, carbonates,
bicarbonates and metallic cyanides. The number of compounds of carbon is greater than the
number of compounds of other elements in the periodic table put together.
UNIQUENESS OF CARBON
Carbon is able to form more compounds than the other elements because;
1. It forms very strong covalent bond with itself (catenation) to form straight or ring system
2. It forms very strong covalent bond with other elements e.g. oxygen, nitrogen etc.
3. It forms multiple covalent bond with itself and some other elements e.g. oxygen, nitrogen
4. It is tetravalent

HYBRIDIZATION IN CARBON
This is the mixing/blending of 2s and 2p orbitals to form hybrid/equivalent orbitals.
Illustration
Atomic number = 6
Orbital electronic configuration = 2, 4
Sub-orbital electronic configuration = 1s2 2s2 2p2

1s2 2s2 2p2

Ground state electronic configuration

 1s2 2s1 2p3

Excited state electronic configuration

There are three ways by which carbon can blend the 2s and the 2p orbitals
1. sp3 hybridization: this involves the mixing of 2s and three 2p orbitals.

+ + + =

s py px pz sp3

The sp3 hybrid orbitals formed is tetrahedral in shape and has bond angle of 109°
2. sp2 hybridization: this involves the mixing of 2s and two 2p orbitals.

+ + =

s py px sp2

The sp2 hybrid orbitals formed is trigonal planar in shape and has bond angle of 120°
3. sp hybridization: this involves the mixing of 2s and one 2p orbitals.

+ =

s py sp

The sp hybrid orbitals formed is linear in shape and has bond angle of 180°

BOND FORMATION IN ORGANIC COMPOUNDS

This involves overlapping of orbitals which results into sharing of electrons, hence bond
formation. There are two types of bonds in organic compounds
1. Sigma bond (σ): This is formed when there is linear overlapping of orbitals e.g. s and s, p and
p, sp3 and s, sp3 and p, sp3 and sp3 etc.
2. Pi bond (π): This is formed when there is parallel overlapping of orbitals e.g. p and p orbitals

NOTE: Sigma bond is stronger than pi bond because the degree of overlapping in sigma bond is
greater than that of the pi bond.
Illustration
Ethane
H H 6 C H = sp3 and s orbitals

H C C H 1 C C = sp3 and sp3 orbitals

H H 7
There are seven sigma bonds and no pi bond in ethane molecule

Ethene sigma bond

H H 2
4 C H = sp and s orbitals
C C 1 C C = sp2 and sp2 orbitals
H H 5
pi bond

1 C C = p and p orbitals
There are five sigma bonds and one pi bond in the molecule
 Ethyne sigma bond
2 C H = sp and s orbitals
H C C H 1 C C = sp and sp orbitals

3
pi bond

2 C C = p and p orbitals
There are three sigma bonds and two pi bonds in the molecule
NOMENCLATURE, HOMOLOGOUS SERIES AND FUNCTIONAL GROUPS’ CHEMISTRY
Nomenclature is the naming of organic compounds and this can be categorized into two: (i)
systematic (IUPAC) and (ii) non-systematic (common or trivial).

i. Systematic (IUPAC) naming: The IUPAC names of aliphatic (straight chain) alkanes form the
basis of IUPAC nomenclature for other classes of the organic compounds. The table below gave
the number of carbon atom(s), names of the straight chain alkanes, their corresponding
condensed structures of the first twenty members of the homologous series.
Number of Name of the Condensed Number of Name of the Condensed
carbon atom straight chain structure carbon atom straight chain structure
1 methane CH4 11 undecane CH3(CH2)9CH3
2 ethane CH3CH3 12 dodecane CH3(CH2)10CH3
3 propane CH3CH2CH3 13 tridecane CH3(CH2)11CH3
4 butane CH3(CH2)2CH3 14 tetradecane CH3(CH2)12CH3
5 pentane CH3(CH2)3CH3 15 pentadecane CH3(CH2)13CH3

6 hexane CH3(CH2)4CH3 16 hexadecane CH3(CH2)14CH3

7 heptane CH3(CH2)5CH3 17 heptadecane CH3(CH2)15CH3

8 octane CH3(CH2)6CH3 18 octadecane CH3(CH2)16CH3

9 nonane CH3(CH2)7CH3 19 nonadecane CH3(CH2)17CH3

10 decane CH3(CH2)8CH3 20 eicosane CH3(CH2)18CH3

It should be noted that each alkane differs from the preceding one by one CH2 group. A series of
compounds like this, where each member differs from the next member by a constant unit, is
called a homologues series. Members of a homologues series are called homologs e.g. alkenes,
alkynes, haloalkanes, alkoxyalkanes, alkanols, alkanals, alkanones, alkanoic acids,
alkylalkanoates, alkanamide, alkanamines etc. each forms homologues series.

For other classes of organic compounds, the last letter “e” of alkane is replaced by a group of
letters e.g. “ol” replaces “e” of alkane to give alkanol, “al” replaces “e” to give alkanal, “one”
replaces “e” to give alkanone, “amine” replaces “e” to give alkanamine, “oic acid” replaces “e”
to give alkanoic acid but “ane” of the alkane is replaced by “ene” and “yne” to give alkene and
alkyne respectively.

ii. Non-systematic (common or trivial) naming: These are the names some organic compounds
were called before the advent of IUPAC nomenclature. Though IUPAC nomenclature was
established for standardizing nomenclature for all types of organic compounds but common
names of some organic compounds are still retained e.g. formaldehyde (methanal), acetone
(propanone), acetic acid (ethanoic acid), acetylene (ethyne), ethylene (ethene), chloroform
(trichloromethane), tartaric acid (2,3-dihyroxylbutan-1,4-dioic acid) etc.
A functional group is part of an organic compound that influences and effectively determines the
compound’s chemical and some of the physical properties.
TYPES OF ORGANIC REACTIONS
1. Substitution reaction: This is a reaction in which an atom or a group of atoms attached to a
carbon atom is replaced by another. This reaction occurs in saturated organic compounds e.g.

CH4 + Cl2 CH3Cl + HCl

CH3CH2Br + H2O CH3CH2OH + HBr

Because of the stability of benzene ring, it undergoes substitution reaction rather than addition
reaction.

AlCl3
C6H6 + Cl2 C6H5Cl + HCl
Conc. H2SO4
C6H6 + HNO3 C6H5NO2 + H2O
90 C
2. Addition reaction: This is a reaction in which the number of atom or group of atoms attached to
a carbon atom increases. This reaction occurs in unsaturated organic compounds e.g.
Ni
CH2=CH2 + H2 CH3-CH3
Pd
CH=CH + 2 H2 CH3-CH3

Ni
+ H2
3. Elimination reaction: This is a reaction in which the number of atom or group of atoms
attached to a carbon atom decreases. The degree of unsaturated in the organic compound
increases e.g.

Conc. H2SO4
CH3CH2OH CH2=CH2 + H2O
alcoholic
CH3CH2Br CH2=CH2 + NaBr + H2O
NaOH

4. Rearrangement reaction: This is a reaction in which an atom or a group of atoms migrate from
one site to another within the same molecule e.g.
migration
CH3-CH-CH=CH2 CH3-CH=CH-CH2-Cl
of
Cl function group

CH3 CH3
H3C C CH2-Cl rearrangement
of H3C C CH2-CH3
CH3 carbon skeleton Cl

CH3 CH3
H3C C CH=CH2 H3C C C-CH3
CH3 H3C
ISOMERISM
This is the occurrence where two or more compounds have the same molecular formula but
different structural formula. Isomerism is divided as shown in the chart below;

ISOMERISM

Structural (Constitutional) Stereoisomerism

skeleton positional functional group tautomerism geometrical optica

or l
chain

❖ Structural or constitutional isomerism;

This type of isomerism involves the order of atoms connectivity within the compounds i.e.
the way the atoms are connected to one another is different from one compound to the other
and this type of isomerism is divided into skeleton (chain), positional, functional group and
tautomerism.
• Skeleton (Chain): Here we talk about straight chain and branched chain isomers e.g.
butane and 2-methylpropane
 CH3

CH3-CH2-CH2-CH3  CH3-CH-CH3
butane 2-methylpropane
The two compounds have the same molecular formula, C4H8, but different structures

• Positional: Here the isomers belong to the same class of organic compound but the
position of the functional group is different in the compounds e.g. pentanol and 2-
pentanol

OH

CH3-CH2-CH2-CH2-CH2-OH  CH3-CH-CH2-CH2-CH3
pentanol 2-pentanol
The only difference in the compounds is just the position of the functional group.

• Functional group: Here the isomers belong to different classes of organic compounds
e.g. ethanol and methoxymethane

CH3-CH2-OH  CH3-O-CH3
ethanol methoxymethane
 • Tautomerism: Here the isomers belong to different classes of organic compounds but are
in dynamic equilibrium with each other e.g. enols and carbonyl compounds.

H H H O
C C H C C
H OH H
H
Ethenol Ethanal

❖ Stereoisomerism;
This type of isomerism does not involve the order of atoms connectivity within the
compounds actually the order of atoms connectivity remain the same but the spatial
arrangement of the atoms differ from one compound to the other and this type of isomerism
is divided into geometrical and optical isomerism.

• Geometrical: This type of isomerism occurs where rotation between carbon atoms is
restricted and this can be seen in alkenes and cycloalkanes e.g. but-2-ene and 1,2-
dichlorocyclohexane.
Consider but-2-ene,
 H CH3 H CH3
C C

C C
H CH3 H3C H
I II
Between carbon 2 and 3 rotation is not possible therefore the methyl groups on carbon 2 and 3 in
structure I are on the same side while that of structure II are on the opposite side. The two
structures are not the same, I is cis- form (Z configuration) while II is trans- form (E
configuration) of but-2-ene.
Consider 1,2-dichlorocyclohexane,
Cl Cl
Cl Cl


I II

Rotation is also restricted in alicyclic alkanes unlike in aliphatic alkanes. Therefore the two
chlorine atoms in structure I are on the same side of the plane while that of the structure II are on
the opposite side of the plane of the compound. The two structures are not the same, I is cis- form
(Z configuration) while II is trans- form (E configuration) of 1,2-dichlorocyclohexane.
• Optical: This type of isomerism occurs when two compounds of the same molecular
formula and the same order of atoms connectivity but different spatial arrangement of
the atoms rotate plane polarized light in opposite directions. Compounds that exhibit this
property must have stereo-centre/chiral centre.