1

LECTURE 1
Historical Development of Organic Chemistry

As the knowledge of chemical compounds increased, some scientists were

quick to draw a dividing line between the known chemical compounds
according to their sources. Namely, those obtained from biological sources
and those obtained from non-biological sources (mineral or inorganic
sources).
It was believed by these early scientists that there seems to be an essential
yet inexplicable difference between the properties of these two groups of
compounds. That the substances of biological origin cannot be synthesized
outside of living cells. In other words, an essential living force (vitalism) was
necessary to "assemble" the molecules that were of biological origin. This
led to the proposal of the vital force theory, which was accepted to account
for the "believed” differences that existed between the two groups of
compounds. The term “organic chemistry" was coined by Berzelium,
Gevela Jacob for the study of compounds of biological origin.

Later on, the successful synthesis of urea (a known organic substance)

from ammonium cyanate by Wohler put down the vital force theory.

What is organic chemistry?

Organic chemistry was originally defined as the chemistry of biological
molecules. However, it has been redefined as the chemistry of carbon
compounds.
General properties of organic compounds
(1) Most organic compounds are either gases, low boiling liquids or solids
with low melting points.
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(2) They are generally insoluble in water but dissolve in non-polar solvents.

(3) Organic compounds burn easily (flammable) and burn to give mainly
carbon(IV)oxide and water.

(4) They exist as covalent molecules and their solutions are non-conductors
of electricity.

(5) As a result of the ability of carbon to bond to other carbon atoms

(catenation), most organic compounds exhibit isomerism.

(6) Chemical reactions involving organic compounds are generally slow and
require long times for completion. As a result, organic reaction mixtures
usually contain large quantities of unreacted materials. This requires
elaborate methods of purifications to obtain pure reaction products

Sources of Organic Compounds

Organic compounds are obtained from the following sources.

1. Plant and animal tissues where they are isolated using suitable
solvents.
2. Natural gas and petroleum
3. Coal
4. From synthetic sources.
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Lecture (2)
Isolation and Purification of organic compounds

Organic compounds are isolated (extracted) from their sources using

suitable solvents/ solvent mixtures of varying polarities. These extracts and
most synthetics organic compounds are seldom pure. For this reason, the
extracts are subjected to various purification processes in order to remove
the impurities, which will interfere with their chemical reactions and structure
determinations.

Purification methods
The method used to purify an organic compound, depends on

(i)The nature of the compound (liquid, solid or gas)

(ii)The nature of the impurities present in the compound.The under listed

methods are used to purify organic compounds:

(1) Crystallization (2) sublimation (3) Various forms of distillation (fractional

distillation, distillation under reduced pressure, steam distillation) (4) solvent
extraction
(5) Various types of chromatography [column, gas, paper and thin layer
chromatography].

LECTURE 3

Qualitative/Quantitative analysis of organic

The extraction and purification of an organic compound is followed both

qualitative and quantitative analyses.
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Qualitative Analysis
This involves both elemental analysis and functional group analysis of
organic compounds.

Elemental Analysis
The elemental analysis of an organic compound involves the use of certain
reactions to identify the elements present in the compound. Since carbon
and hydrogen are always present in all organic compounds, there is no
need for their analysis. The elements usually analyzed for are the halogens,
sulphur, nitrogen and phosphorus. The presence of any or some of these
elements in an organic compound is an indication of the presence of certain
"functional groups" in the compound.
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Examples
(i) The presence of nitrogen indicates the presence of nitrogen-containing
functional groups such as amines, amide, cyano or the nitro-group.

(ii) The presence of sulphur indicates either the presence of sulphonic acid
or thio compounds.

(iii)The presence of halogen(s) indicates the presence of either alkanoyl,

alkyl or aryl halides
The result obtained in the course of elemental analysis serve as a guide for
more specific tests in functional group analyses.

Theory of elemental analysis

The usual organic reactions are unable detect the halogens, nitrogen,
sulphur or phosphorus that may be part of an organic molecule. This is due
to the covalent nature of the bonds in organic molecules. The usual method
is to convert the above elements into compounds containing inorganic ions
that will respond to the usual inorganic qualitative tests.
Procedure
The organic compound is heated with sodium metal (fusion). This process
converts sulphur into sodium sulphide (Na2S), nitrogen into sodium
nitrile(NaCN) and the halogens to sodium halides(NaX).

These reactions can be represented by the following general equation:

When both nitrogen and sulphur are present in the same sample, there is
the possibility of forming sodium thiocyanate (NaCNS). For this reason, it is
always necessary to use an excess of sodium metal which will further react
with the sodium thiocyanate to form the desired products.
 6

Test for sulphur

Place about 2 cm3 of the fusion filtrate in a test tube, add 3 drops of freshly
prepared 1% disodium pentacyano nitrosyl ferrate (II) (sodium
nitroprusside). The development of a purple colour which slowly fades on
standing indicates the presence of sulphur in the test sample.
Test for nitrogen
Transfer 2cm3 of the fusion filtrate into a test-tube and add a few drops of
freshly prepared iron(II) tetraoxosulphate (VI) solution. Boil the reaction
mixture for about one minute. Remove from flame and cool the test tube
under a running tap. Add two drops of iron (II) chloride solution, followed by
two drops concentrated hydrochloric acid. The development of greenish
blue colouration or precipitate of Prussian blue indicates the presence of
nitrogen in the test sample.

Test for Halogens

Transfer 2 cm3 of the fusion filtrate into a clean test-tube. Acidify with a few
drops of dilute trioxonitrate (V) acid. Boil the reaction mixture for 3 minutes
(preferably in a fume cupboard). This is to remove all cyano (CN-) and
sulphide (S2-) ions as hydrogen cyanide and hydrogen sulphide respectively
if sulphur and nitrogen are present. After the heating, add to the test tube a
few drops of dilute aqueous silver trioxonitrate (V) solution. The formation of
a precipitate indicates the presence of a halogen in the test sample.
Possible Results
(i) A white precipitate soluble in excess of ammonia solution indicates
the presence of chlorine.
(ii) A pale-yellow (cream) precipitate soluble in an excess of
concentrated ammonia solution indicates the presence of bromine.
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(iii) A yellow precipitate insoluble in an excess of concentrated

ammonia solution indicates the presence of iodine in the test
sample.

Test for Phosphorus

Place 2 cm3 of the filtrate in a clean test tube. Add a few drops of
concentrated trioxonitrate (V) acid. Allow the reaction mixture to cool and
add 2 cm3 of ammonium molybdate reagent and warm. The formation of
yellow crystalline precipitate indicates the presence of phosphorus in the
test sample.
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Lecture 4
CHEMICAL FORMULAE
The chemical formula of an organic compound is the short-hand
representation of one reacting unit of the compound showing the elements
present and their numbers. The chemical formula of a compound is a
representation of one reacting unit of the substance using symbols and
numbers to indicate the elements and their numbers present. There are
three levels of chemical formulae in organic compounds namely: - empirical,
molecular and structural formulae.
EXAMPLE
The formula of ethanol, a popular constituent in most alcoholic beverages is
C2H6O. This formula shows that one reacting unit of ethanol contains two
atoms of carbon, six atoms of hydrogen and one atom of oxygen.

A close look at the formulae of some organic compounds, show that two or
more compounds can be represented by the same formula. This shows that
obtaining the formula of a compound via chemical analyses is not adequate
for us to identify it. Examples abound in organic chemistry where two or
more compounds have the same number of atoms in their molecules but
show different reactions. Ethanol and methoxy methane. 1. Both
compounds have the molecular formula C2H6O.
Empirical formula
The empirical formula of a compound shows the constituent elements in
one reacting unit of the compound in their relative numbers (simplest ratio).

Molecular formula
The molecular formula of a compound is the chemical formula that shows
the actual numbers of each kind of element present in one reacting unit of
the compound. This formula is usually a whole number multiple of the
empirical formula.
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Calculation of the empirical and molecular formula

The empirical and molecular formulae of chemical compounds are
calculated from information obtained from their quantitative elemental
analyses (elemental composition of the compounds).
Example
An organic compound on analysis was found to contain 10.06% of carbon,
0.84% of hydrogen and 89.10% of chlorine. Calculate its empirical formula.

Solution:

(i) Divide the % composition of each element by its atomic mass.

C= 10.06/12 = 0.838; 0.84/ 1 =0.84 ; 89.10/ 36.6 = 2.43

(ii) Divide the numbers obtained by the smallest number.

0.838/0.838 = 1; 0.84/0.838= 1; 2.43/ 0.84 = 3.

The ratio of the numbers indicates the empirical formula of the
compound.

Empirical formula: CHCI3

Structural formula:

The structural formula of a compound is the formula that shows the atoms,
groups, bond and their relative arrangement within the compound. In other
words, the structural formula in addition to the types of elements and their
numbers present in a compound also shows the connectivity of the atoms
and groups present.

Examples:
 10

The molecular formula, C3H6O can represent each of the following

compounds: -

CH3CH2CHO CH3COCH3
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2. The molecular formula C3H8O can represent each of the following

compounds: -

CH3CH2CH2OH CH3CH2OCH3
The above examples show that the structural formula can be used to predict
both the physical and chemical properties of a compound.
Types of structural formulae
There are four types of structural formulae namely:

Condensed structural formula, graphical structural formula, bond-line

structural formula and wedge structural formula.
Condensed Structural formula
In condensed structural formulae, the carbon atoms that form the molecule
are written in a linear arrangement. All the atoms attached to a given carbon
atom follow after it before the adjacent carbon. This is illustrated by the
structures below:

CH3CH2CH2NH2 CH3CH2CONH2
Graphical
This type of structural formula displays the actual linkages of atoms and
groups within the molecule.

In graphical structures, each line connecting two atoms represents a shared

pair of electrons. Graphical structures also clearly show the valencies of the
various atoms in a compound. For example, each bond (line) emanating
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from an atom represents one valency. In the above structures, carbon is

linked by four bonds (lines) which clearly shows it has a valency of four.
Similarly, the oxygen atoms are linked by two lines while the hydrogen
atoms are linked by one line each.

Bond line structure (Structure formula)

In bond-line structures, only lines are used to represent the structures of

hydrocarbons. The convention here is that any vertex and terminus is a
carbon atom. The hydrogen atoms are not shown.

Wedge structural formula

Since the bonds in organic structures are directional, the wedge structural
formula indicates the spatial orientation of the bonds around each carbon
atom. Usually bonds in the plane of the paper are shown by normal lines,
the bonds below the plane of the paper by broken lines and the lines above
the plane of the paper with thick (bold) lines.

Examples:
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Lecture 5
BONDING IN ORGANIC COMPOUNDS
Carbon is the central atom in the structures of all organic compounds and
its mode of bonding (covalency) is reflected in their molecules. Covalent
bonds are formed through the overlapping of atomic orbitals in the
uttermost shells of the participating atoms.
Atomic Structure of carbon
C (6)1S22S22P1X2P1Y
This electronic configuration shows carbon has only two unpaired electrons
and is expected to form two covalent bonds. On the contrary, carbon
exhibits a valency of four in most stable organic structures. The tetra
valency of carbon is accounted for by carbon “making available" four
unpaired electrons through the unpairing of the 2s electrons with the
subsequent promotion of one of them to the 2pz level.

C* (6)1S22S12P1X2P1Y 2P1Z

The directional nature of the bonds in organic structures (their shapes) is

accounted for by the theory of hybridization of atomic orbitals. Carbon
atoms hybridize their 2s and three 2p atomic orbitals in various modes to
produce three types of hybrid orbitals
 14

Carbon atoms in organic compounds form bonds through the overlap of

these hybrid orbitals with themselves, the overlap of unhybridized p-orbitals
and the overlap of hybrid orbitals with orbitals of other atoms (hydrogen,
oxygen nitrogen the halogens and sulphur).

sp3 hybridization in carbon atoms.

The sp3 hybridization of carbon atoms involves the blending of the 2S and
the three 2P-oribitals (2Px,2Py and 2Pz, structure 4) to obtain a set of four
new orbitals referred to as sp3 hybrid orbitals.

Each sp3 hybrids orbital has 25% s-character and 75% p-character. These
orbitals are directed towards the corners of a tetrahedron. They are used to
overlap with other sp3 hybrid orbitals from other carbon atoms and 1s
atomic orbitals of hydrogen atoms to give sigma bonds as in alkane
structures.

SP2 HYBRIDIZATION IN CARBON ATOMS.

The sp2 hybridization of carbon atoms involve the blending together of the
2S atomic orbitals and two 2P orbitals (2Px and 2Py) to produce a set of
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three new orbitals referred to as sp2 hybrid orbitals. This mode of

hybridization leaves one unhybridized P orbitals in the carbon atom.

The three sp2 hybrid orbitals are directed towards the corners of an
equilateral triangle separated at 120o. These hybrid orbitals can be used to
overlap with other sp2 hybrid orbitals and 1s atomic orbitals of hydrogen to
form sigma bonds.

Formation of carbon-carbon double bonds in alkenes:

The alkene double bond consists of one sigma bond and one pii-bond. Each
of the carbon atom of the double bond have three sp2 hybrid orbitals, that
are used in overlapping with 1s atomic orbitals of two hydrogen atoms and
an sp2 hybrid orbital of the other carbon atom. This leaves one unhybridized
p-orbital on each of the carbon atoms.
 16

As noted earlier, the overlap between the sp2 hybrid orbitals produce sigma
bonds. The unhybridized p-orbitals in the carbon atoms overlap in a lateral
direction (sideways) to produce the pii-bond between the two carbon atoms.
This bond is weaker than the sigma bond and is easily broken in the course
of a reaction. This explains why the alkenes which contain pii-bonds are
more reactive than the alkanes.

SP-HYBRIDIZATION IN CARBON.

The sp-hybridization of carbon atoms involve the blending together of the 2s

atomic orbital and one 2p atomic orbital to give two sp hybrid orbitals. This
leaves two unhybridized 2p atomic orbitals on the carbon atom.

During the formation of the carbon-carbon triple bond in alkynes, each of

the carbon atoms use one sp hybrid orbital to overlap with the sp hybrid
orbital of an adjacent carbon atom and the other to overlap with a 1s atomic
orbital of a hydrogen atom producing sigma bonds. Each carbon atom has
two unhybridized p-atomic orbitals that overlap laterally with those of the
adjacent carbon atom to give two pii-bonds. This in addition to the sigma
bond formed via the overlap of the sp hybrid orbitals constitute the triple
bond between the two carbon atoms.
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Lecture 6

STRUCTURES OF ORGANIC COMPOUNDS.

The structure of an organic compound is the arrangement of bonds, atoms

and groups within the compound (molecule). In other words, the structure of
a compound shows the number and types of elements (atoms) present in
the molecule together with the connectivity of the atoms/groups in the
compound. This is explained further under the different types of chemical
formulae.
The structures of organic compounds can be viewed as formed by the
linking together of carbon atoms to give some basic skeletons (frame
works). The other atoms such as hydrogen, oxygen, sulphur, nitrogen and
the halogens are attached to the basic skeleton(s) to complete the
structures. The hydrocarbons contain only carbon and hydrogen atoms in
their molecules and have the simplest structures among organic
compounds. Their basic structures consist of a frame work of carbon atoms
via different connectivities. The carbon atoms are bonded to each other
either by single or multiple bonds depending on the class of hydrocarbon.
For example, the carbon atoms in alkanes are linked together by single
bonds, giving them the following basic structural patterns:

(i)A chain of carbon atoms linked to each other via single bonds to give a
basic skeleton.

(ii)The attachment of hydrogen atoms to the basic skeleton to complete the

valencies of the carbon atoms.

EXAMPLES:

Possible frameworks of organic structures containing of four carbon atoms.

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Frameworks containing five carbon atoms

The above frameworks show four types of carbon atoms: -

(i)Carbon atoms that are bonded only to one other carbon atom. These are
referred to as primary carbons.

(ii) Carbon atoms that are bonded to two carbon atoms. Such carbon atoms
are referred to as secondary carbon atoms.

(iii)Carbon atoms that are bonded to three carbon atoms. Such carbon
atoms are called tertiary carbon atoms.
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(iv)Carbon atoms that are bonded to four carbon atoms. Such carbon atoms
are called quaternary carbon atoms.
Examples
Classification of organic compounds
Due to the large number of organic compounds it is necessary to classify
them into manageable groups. Several modes of classification are known.
The most effective methods rely on some structural features of organic
compounds such as:

(i) The carbon skeletons

(ii) The functional groups present in the molecules.
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Classification according to carbon skeleton

This mode of classification groups the organic compounds into two groups
as:

(i) The aliphatic compounds (open chain organic compounds).

(ii) The cyclic organic compounds.

The Aliphatic Organic Compounds

As noted above, the carbon atoms in this group of organic compounds are
in open chains. They are further sub-divided into groups as saturated and
unsaturated depending on whether their carbon chains contain multiple
bonds or not. The unsaturated aliphatics contain multiple bonds in carbon
chains while the saturated aliphatics do not have multiple bonds in their
carbon chains.
Examples

Another sub-division of aliphatic compounds is based on whether the

carbon chains of the compounds are either branched or unbranched.
Examples

The Cyclic Organic Compounds

The organic compounds in this group have either all or most of their carbon
atoms in a ring structure. They are sub-classified into three groups as
alicyclic, aromatic or heterocyclic compounds.
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Alicyclic compounds
These are cyclic organic compounds that have only carbon atoms in their
rings. They are also called carbocyclic compounds.

Examples.

Cyclobutane Cyclopentane.
Aromatic Compounds
These are cyclic organic compounds that have conjugated pii-bonds in their
rings, with the number of pii-electrons conforming to the Huckel’s rule.
Benzene is the most common example.

Heterocyclic Compounds
These are cyclic organic compounds that their ring structures contain other
atoms such as nitrogen, oxygen or sulphur in addition to carbon atoms.
Examples
 23

Furan Pyrrole Thiophene Pyridine

Classification according to Functional groups

The reaction patterns observed in organic compounds indicate that organic
reactions depend on the presence of specific atoms, group of atoms or
bonds within a given compound. These reactive spots are referred to as
functional groups.
Functional Group
A functional group is either an atom, group of atoms or a bond that is part
of a larger molecule and has characteristic chemical reactivity.

The following table lists some of the common functional groups, their
structures and the organic compounds they occur:

STRUCTURE OF FUNCTIONAL NAME OF NAME ENDING

GROUP COMPOUND
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Alkene -ene

Alkyne -yne

Arene

Halides Halo-

Alcohol -ol
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Ether Ether

Amine -amine

Nitrile -nitrile

Aldehyde -al

ketone -one
26

Carboxylic acid -oic acid

Ester -oate

Amide -amide

Acid Chloride -oyl chloride

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Carboxylic acid -oic anhydride

anhydride

Since each functional group undergoes characteristic reactions, by

recognizing the functional group in a molecule, it is possible to predict the
reactions of any compound.

Example: Both ethene and menthene contain the carbon-carbon double

bond and undergo similar reactions.

Ethene Menthene
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Generally, the chemistry of every organic molecule, regardless of size and

complexity is determined by the functional groups it contains. As a result, it
is possible to classify organic compounds into families using the functional
groups they contain.
Uses of functional groups
(i) The functional groups form the basis of naming organic compounds.
(ii) The functional groups serve as a convenient means of classifying
organic compounds into classes (families, homologous series).
(iii) The functional group is the site of reaction in all compounds.
Therefore, all compounds containing the same functional group will
undergo similar reactions (show similar chemical properties).
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Lecture 7
Types of organic reactions and factors that affect organic reactions
The substrate / reagent concept of organic reactions

Goto my pictures and LT7 into application.

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Lecture 8

ALIPHATIC ALKANES
The aliphatic alkanes are open chain hydrocarbons containing only carbon-
carbon single bonds. Their carbon chain can either be branched or
unbranched.

Examples:

i.Alkanes with unbranched carbon chains:

Alkanes with branched carbon chains

All aliphatic alkanes containing four or more carbon atoms can exist in both
branched and unbranched carbon chain structures. In other words, they can
exhibit structural isomerism.

2-methyl butane 2,2-dimethyl propane

Question:

Use the molecular formula C6H14 to draw the structures of three branched
chain hydrocarbons.

Nomenclature of aliphatic alkanes.

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The name of an organic compound is made up of two parts: - The prefix,

(stem/root) and the suffix. The prefix of the name indicates the number of
carbon atoms and the number/nature of the branches (alkyl substituents) if
any, present in the structure of the compound.

On the other hand, the suffix of the name indicates the homologous series
the compound belongs to. (See classifications).
The following table shows the prefixes for alkanes containing one to ten
carbon atoms in their molecules.
Number of carbon atoms Prefix
i.one meth

ii.two eth

iii.three prop

iv.four but

v.five pent

vi.six hex

vii.seven hept

viii.eight oct

ix.nine non

x.ten dec

The suffix of the alkanes is -ANE. Attaching each of the above prefixes to
the group suffix gives the name of the alkane with the corresponding
number of carbon atoms.
Examples
CH3CH2CH2CH3
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This alkane contains four carbon atoms and the prefix is but; attaching the
group suffix - ane to but gives the name butane

(ii)

This alkane also contains four carbon atoms in its structure and is also a
butane. The actual name of this compound is 2 – methyl propane. In order
to avoid confusion, a comprehensive set of rules are followed to
unambiguously name the aliphatic alkanes.

(i) Locate the longest continuous chain of carbon atoms in the structure and
obtain a base name.

(ii) Locate the nature and number of the different alkyl substituents present
in the structure of the alkane.

(iii) Identify the substituents.

(iv) Use the position numbers and names of the substituents as a prefix to
the base (parent) name. The numbers and names are separated by a
hyphen.

(v) Identify the substituent by name and position number when the same
substituent occurs more than once in the same molecule. Use the prefixes
di, tri or tetra to indicate their number.

Example:
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2,3-di methyl butane

2, 2-dimethyl propane

(vi) When two or more different substituents are present, their names are
arranged in alphabetical order and added to the parent name of the alkane.
All are written as one word.

Examples:

3-bromo, 3-Methylpentane
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Physical Properties
The alkanes are non-polar and non-associated compounds. This is
illustrated by their physical properties.

(i) The first four members are gases while those containing five to
seventeen carbon atoms are liquids. Those containing 18 or more carbon
atoms are waxy solids.

(ii) Due to their non-polar nature, alkanes are insoluble in polar solvents
such as water but soluble in non-polar solvents such as chloroform and
benzene.

(iii) All aliphatic alkanes have densities less than that of water. The densities
increase with molar masses. Their boiling and melting points increase with
molar masses. Branching of the carbon chain decreases boiling points.

Chemical Reactions
The alkanes are relatively stable compounds due to their non-polar nature.
Under normal conditions they are not attacked by acids, bases or common
oxidizing agents. Despite their unreactive nature alkanes undergo some
reactions under high temperatures or when exposed to sunlight/ultra-violet
radiation.
The normal reactions are
i.Substitution reactions

ii.Oxidation reaction in form of combustion

Substitution Reactions
The substitution reactions involve the replacement of one or more hydrogen
atoms in the molecule of an alkane with other atoms or groups in a reaction.
 35

The common substitution reactions of alkanes include halogenation,

nitration and sulphonation.

Halogenation
The halogenation of alkanes is a reaction in which the hydrogen atoms of
an alkane are replaced with halogen atoms (chlorine or bromine).

These reactions occur in the presence of either sunlight, ultra-violet light or

at temperatures between 300-400oC.
The reaction usually gives a mixture of products because more than one
hydrogen atom in the structure can be replaced.
Nitration
The nitration of alkanes involves the replacement of hydrogen atoms of the
alkane with the nitro group (-NO2). This is a gas phase reaction (400-500oC).
The products are nitro-alkanes.

Sulphonation
Alkanes react with fuming sulphuric acid at high temperatures to form
alkane sulphonic acids.
 36

This reaction involves the replacement of the hydrogen atoms of an alkane

with the sulphonic acid group.

OXIDATION (COMBUSTION)

A mixture of alkanes and air (or excess oxygen) on ignition burns to form
carbon (IV) oxide, water and large amount of energy as heat. For example,
methane burns in excess air according to the following equation.

Alkanes undergo partial combustion when the supply of oxygen is

insufficient. The incomplete combustion of alkanes can produce other
products such as carbon(II)oxide, methanol, ethanoic acid or carbon black
as shown by the following equations of reaction.

Advantages/Disadvantages of burning alkanes

The burning of alkanes in air in internal combustion engines is used to drive

engines, generate electric energy in generating sets and gas turbines.
Despite the production of energy from the burning of alkanes is a source of
 37

pollutants such sulphur(IV) oxide and carbon(II) oxide.

 38

LECTURE 9

ALKENES

The alkenes are aliphatic hydrocarbons containing one carbon-carbon

double bond in their structures. Examples:

They form a homologous series with the general formula, CnH2n. This

formula shows that an aliphatic alkene contains two hydrogen atoms less

than the corresponding alkane. A shift in the position of the double bond in

the structure of an alkene produces a different structure. The structure of

butene can be used to illustrate this. That is, the double bond can either be

located at position one or position two.

CH3CH=CHCH3 CH3CH2CH=CH2

Nomenclature of alkenes

The names of simple alkenes are derived from the names of the

corresponding alkanes. The only modification required is to replace the -

 39

ane ending the name of the alkane with – ene. The suffix - ene in the name

of a hydrocarbon indicates the presence of a carbon – carbon double bond.

Generally, the alkenes are named using a set of rules in order to

accommodate all the structural variations.

i. Locate the longest continuous chain of carbon atoms that include

the carbon atoms of the double bond. Obtain the parent (base)

name for the compound.

ii. Number the carbon atoms of the chain starting from the end near

the double bond. Use the number at which the carbon atom

originates to indicate the position of the double bond.

iii. Identify any substituents, their numbers and positions.

iv. The name of the alkene is written by writing the substituents, their

numbers and the number indicating the double as a prefix to the

base name.

Examples: Give the IUPAC names of the following alkenes:

(i) CH3CH=CHCH3 (ii) CH3CH2CHCH=CH2

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Solution:

i. The longest continuous chain contains four carbon atoms with one

double bond.

Parent name: butene. The double bond is located between the C-2

and C-3. Therefore '2' will be used to indicate the position of the

double bond. Name: 2-butene

ii. The longest continuous chain contains five carbon atoms with one

double bond.

Parent name: pentene. One methyl substituent is attached to the

chain therefore; the compound is a methyl pentene.

Numbering of the carbon chain places the double bond at position

one and the methyl group at position three.

Name: 3-methyl-1-pentene.

ISOMERISM IN ALKENES

Alkenes can exhibit both structural and geometrical isomerisms.

Structural Isomerism
 41

Structural isomerism in alkenes can be due to either chain length,

arrangement of substituents or the location of the double bond. The

following compounds

1-pentene 2-pentene

2-methyl-1-butene 3-methyl-1-butene

2-methyl-2-butene.

All the above compounds are structural isomers of the molecular formula,
 42

C5H10. These compounds differ in the positions of their double bonds,

methyl substituents and chain lengths.

Geometrical Isomerism

Some alkenes have the same structures but differ in the arrangement of

groups around their double bonds. Such alkenes exhibit geometrical

isomerism. An example of geometrical isomerism is seen in the structure of

but - 2 - ene.

CH3CH=CHCH3

In this structure, different groups are attached to the double bond carbon

atoms (H and CH3). Since there is no free rotation about the carbon –

carbon double bond, the arrangement of the two groups in space can be in

two different ways as shown below:

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CLASSIFICATION OF ALKENES ACCORDING TO THEIR STRUCTURES

(i) Terminal and non - terminal alkenes.

Alkenes can be classified into two groups as either terminal and non -

terminal alkenes according to the position of the double bond in the

structure of the alkene.

In terminal alkenes, the double is at the end of the carbon chain (position

one) while in non - terminal alkenes, the double bond is within the chain.

Examples:

CLASSIFICATION ACCORDING TO THE PATTERN OF SUBSTITUTION

AROUND THE DOUBLE BOND.

Ethene CH2=CH2is a non- substituted alkene because the carbon atoms of

the double bond bear only hydrogen atoms. When one of the hydrogen
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atoms is replaced by an alkyl group, the alkene is referred to as a mono -

substituted alkene.

Examples:

Similarly, when either, two, three or all four hydrogen atoms are replaced

by alkyl groups, the alkene is classified as di, tri or tetra substituted.

Examples: But-2-ene is an example of a disubstituted alkene.

PHYSICAL PROPERTIES
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The alkenes show similar physical properties to those of the alkanes. The

physical states of the members depend on the number of carbon atoms

contained in their molecules. They are almost insoluble in water but

dissolve in organic solvents.

Chemical Reactions

The alkenes are more reactive than the alkanes due to the presence of the

pii electrons of the double bond in alkenes. These electrons in the pii-bond

are loosely held and can easily be broken in the presence of electron -

loving reagents. This enables the alkenes to undergo addition reactions with

a number of reagents. The products of the reaction are either alkanes or

alkane derivatives depending on the attacking reagent.

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Examples:

(i) Addition of hydrogen

Alkenes react with hydrogen gas under pressure in the

presence of various metal catalysts to form alkanes. Examples

of common catalysts include nickel, platinum and palladium.

The reaction is referred to as catalytic hydrogenation.

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(ii) Addition of halogens

Chlorine or bromine gas dissolved in an inert-solvent e.g.

tetrachloromethane react with alkenes to form dihalogen

derivatives of alkanes. The reaction with bromine is used as a

test for unsaturation due to the change in colour that

accompanies the reaction.

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REACTION WITH POTASSIUM PERMANGANATE SOLUTION (KMnO4)

This reagent reacts with alkenes to give either diols or carbonyl compounds

/ alkanoic acids. The actual product depends on the concentration of the

reagent and/or the reaction conditions.

(i) When treated with dilute cold KMnO4 a diol is formed. In the course of

this reaction the purple colour of the reagent is discharged. For this

reason, the reaction serves as a test for the alkene double bond

(Bayer's Test).

(ii) On the other hand, treating an alkene with hot concentrated

KmnO4, gives oxidative degradative products. With terminal

alkenes an alkanoic acid and carbon (IV) oxide are produced.

With non-terminal alkenes, either two carbonyl compounds, or a

carbonyl compound and an alkanoic acid are produced

depending on the pattern of substitution around the alkene

double bond.
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(iii) Addition of halogen acids (HX; X=Cl, Br, I).

The halogen acids react with the alkenes to form halo-alkanes.

When the structure of the alkene is unsymmetrical, two products

are possible. One of the products predominates. The major

product of the reaction is rationalized by the Markonikov's rule.

Similarly, alkenes react with aqueous solution of the halogen

acids, commonly referred to as hypohalous acids or

bromine/chlorine water. The products of these reactions also

follow the Markonikov's rule.

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(iv) Reaction with H2SO4

When simple alkenes are treated with H2SO4 they react to give

alkyl hydrogen sulphates. The addition gives mainly the

Markonikov’s product when unsymmetrical alkenes are involved.

The alkyl hydrogen sulphates on hydrolysis give alcohols.

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Reaction with Ozone

Alkenes react with ozone in an inert solvent to give ozonides. The

ozonides are very unstable and when treated with zinc and water gives a

mixture of carbonyl compounds.

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Polymerization

When simple alkenes treated with inorganic acid in the presence of

oxygen or with organic peroxides they add to themselves to form large

molecules. The simple alkenes are referred to as 'monomers' while the

product (large molecule) is referred to as a polymer. The reaction is

referred to as polymerization. This reaction is used in the manufacture of

many useful household and industrial materials.

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LECTURE 10

ALKYNES

The alkynes are aliphatic hydrocarbons that contain one carbon-

carbon triple bond in their structures. They form a homologous

series with the general formula, CnH2n-2. This formula shows that

alkynes contain four hydrogen atoms less than the corresponding

alkane. The simplest member contains two carbon atoms with the

formula, C2H2.

Alkynes can also be classified into groups as:

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(i) Terminal and non-terminal alkynes:

(ii) Symmetrical and non-symmetrical alkynes.

TERMINAL ALKYNES

These are alkynes that have their triple bond at a terminal position.

They are also referred to as 1-alkynes.

NON-TERMINAL ALKYNES

The non-terminal alkynes have their multiple bonds at non-

terminal positions.

SYMMETRICAL ALKYNES
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When the structure of an alkyne can be split into two equal halves

at the triple bond, it is referred to as a symmetrical alkyne.

UNSYMMETRICAL ALKYNES

When the structure of an alkyne cannot be split into two

equal parts at the point of the triple bond, the alkyne is

referred to as an unsymmetrical alkyne.

REACTIONS OF ALKYNES
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The alkyne triple bond contains two pii-bonds and one sigma bond.

They undergo addition reactions similar to the alkenes except that

the addition can either be in one step or 2 steps depending on the

reaction conditions.

(i) one step addition gives either an alkene or its derivative

(ii) In a two-step addition either an alkane or its derivative is

produced.

(1) Addition of hydrogen

The reaction occurs in the presence of metal catalysts (Nickel,

Platinum or Palladium). Alkynes add on two moles of hydrogen

molecules to form an alkane.

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The addition can be stopped at the alkene stage using the

Lindlar’s catalyst (Palladium poisoned with BaSO4 and quinoline).

Addition of Halogens

Addition occurs in two steps to give the dihalo-alkene and then the

tetrahalo alkane. The reaction with bromine is used as a test for

the pii

bonds.
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(2) Addition of halogen acids(HX)

The halogen acids add to alkynes to give halogen substituted

alkenes. These can add a second molecule of the halogen acid to

give a dihalo alkanes. The initial product of this reaction is an

unsymmetrical alkene, therefore the addition of the second

molecule of the halogen acid follows the Markonikov’s rule.

(3) Addition of water (hydration)

When treated with a dilute solution of sulphuric acid and mercury

(II) sulphate, alkynes add on water to form an enol. The enol

rearranges to give a carbonyl compound (aldehyde or ketone)

depending on the structure of the alkyne.

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Addition of Hydrogen Cyanide

Hydrogen cyanide adds to ethyne to give vinyl cyanide

(acrylonitrile), the monomer of the synthetic fibre, orlon.

Acetylide Formation

1-alkynes react with reactive metals such as sodium to form metal

acetylides. 1-alkynes also react with ammoniacal solution of

copper (I)chloride and silver nitrate to form their respective

acetylides.
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