Topic Outline

Covalent Bond
- andbond
- Hybridisation
Nomenclature of simple organic compounds
To determine molecular & empirical formula of an
organic compound
Isomerism
- Structural Isomerism
- Types of structural isomerism : Chain,
Position, functional group, tautomerism (ketoenol), metamerism and their effects
- Stereoisomerism : Optical isomerism
(Enantiomerism), Optical Activity, Specific
rotation, racemic mixture, meso compounds,
Diastereomerism,
Geometrical isomerism: Cis-trans and syn-anti
isomerism
Basis of organic reactions
- Polar effects: Inductive effect (+ & - I effect),
electromeric effect, resonace effect
(mesomerism) and aromaticity,
hyperconjugation and their effect on acidity &
basicity and other properties
- Hydrogen bonding
- Intermediates: Carbocation, carbanion, Free
radicals, carbene
1

 Alkanes: Nomenclature, isomerism, preperation,

physical and chemical properties
Alkenes: Nomenclature, isomerism, preperation,
physical and chemical properties
Alkynes: Nomenclature, isomerism, preperation,
physical and chemical properties

COVALENT BOND

For a covalent bond to form, two atoms must be located so that the orbital of one
overlaps with the orbital of another; each orbital must contain a single electron.

When this happens, the two atomic orbitals merge to form two molecular orbitals.
The orbital which is occupied by both the electrons, known as bonding MO. It results
when orbitals with like sign overlap. The electrons are paired in a bonding MO i.e,
they have opposite spins.

This arrangement is more stable than isolated atom; as a result formation of a bond is
always accompanied by the evolution of energy.
This amount of energy per mole is called bond energy or bond dissociation
energy when this amount of energy per mole is supplied to break the bond. (Bond

dissociation energy = - Bond energy)

For a given pair of atoms, greater the overlap of atomic orbitals, stronger is the bond.
If AOs of unlike signs overlap, an anti-bonding MO or MO* results which has a
node (site of zero electron density) between the atoms and therefore has a higher
energy than the individual AOs.

AND BONDS
Head-to-head overlap of AOs give a sigma () MO and the bond is called bond.
The Head-to-head overlap of AOs gives a sigma () MOthe bonds are called
bonds. The corresponding anti-bonding MO* is designated *. The imaginary line
joining the nuclei of the bonding atoms is the bond axis, whose length is the bond
length.

Two parallel p orbitals overlap side by side to form a pi () bond or a * bond. The
bond axis lies in a nodal plane (plane of zero electronic density) perpendicular to the
cross-sectional plane of the bond. Single bonds are bonds. A double bond is one
and one bond. A triple bond is one and two bonds a x and a y, if the triple bond
is taken along the z-axis).

Although MOs encompass the entire molecule, it is best to visualize most of them as
being localized between pairs of bonding atoms. This description of bonding is called

linear combination of atomic orbitals (LCAO).

Stabilities of molecules can be related to the bond order (B.O.), defined as
(Number of valence electrons in MOs) (Number of valence electrons in
MO*s)

B.O. =

__________________________________________________________________
2

The bond order is usually equal to the number of and bonds between two atoms
in other words, 1 for a single bond, 2 for a double bond, 3 for a triple bond.
Difference between and bonds
bond

bond

1. Formed by head-to-head overlap of

1. Formed by lateral/sideways overlap of

AOs.

p /d orbitals

2. Has cylindrical charge symmetry

2. Has maximum charge density in the

cross-sectional plane of the

about bond axis.

orbitals
3. Has free rotation.

3. Does not have free rotation.

4. Only one bond can exist between two

4. One or two bonds can exist between

atoms.

two atoms.

Order of Energy
< < * < *
Hybridisation of atomic orbitals of carbon
AOs of carbon hybridise in three ways:
In case of Alkanes like methane, four equivalent orbitals are formed by blending the

2s and the three 2p AOs give four new hybrid orbitals, called sp3 HOs.
In case of double bond or as it can be seen in alkenes, three equivalent orbitals are
formed by blending the 2s and the two 2p AOs to give three new hybrid orbitals,

called sp2 HOs and similarly for triple bonded carbons as in alkynes, two equivalent
sp hybrid orbitals are formed by mixing of one 2s and one 2p orbital.

Only bonds and lone pair of electrons, not bonds, determine hybridisation &

molecular shapes.
Repulsion between pairs of electrons causes these HOs to have the maximum bond
angles and geometries. (For more details refer to chapter on Bonding)

TYPE OF
HYBRIDISATION

BOND
ANGLE

GEOMETRY

sp3

109.5

Tetrahederal

sp2

120

Triangular
Planar

sp

180

Linear

Tetrahederal geometry of methane

NOMENCLATURE OF SIMPLE ORGANIC COMPOUNDS

Key to naming: Prefix+root word+suffix
Where, prefix: substituent
Root word: parent chain and no. of carbon atoms in it
Suffix: functional group
Position of the substituent and functional groups is given by giving the carbon no. on
which it is present just before the prefix and suffix for that particular substituent and
functional group.
functional group/suffix
H3C-CH-CH2-CH2-CH2-OH
CH3 3-Methyl-butan-1-ol

Root word - but

substituent/Prefix
If there is more than one substituent present, then the prefixes are written in
alphabetical order.
substituent/Prefix
1

functional group/suffix

Cl

Root word - but

H3C-CH-CH-CH2-CH2-OH
CH3 2-Chloro-3-methyl-butan-1-ol

substituent/Prefix 2
If two substituents are present on equivalent position then the lower no. is given to the
one coming first in alphabetical order.
substituent/Prefix
1
Cl

H3C-CH-CH2-CH-CH3
CH3 2-Chloro-3-methyl-butane

substituent/Prefix 2

if there are more than one functional group present, then the compound is named after
the functional groups which is of highest priority (order of priority is given by
IUPAC) and numbering on parent chain is done on such way that the principal
functional group gets the lowest possible no. The rest of the functional groups are
treated as substituents and written as prefixes. E.g.
H3C-CH-CH=CH-CH2-OH
Principal functional group
Br

3-Bromo-but-2-en-1-ol

substituent
But some of the functional groups are treated as substituents and are written like

Halo-, cyano- etc.

Cl

e.g. 2-chloropropane
For Straight chain hydrocarbons
The name is based on the chain str. of the compound. Suffix is ane for alkanes, ene for
alkene and yne for alkyne.
Prefix indicationg the no. of carbon atoms is given:
1 Meth
2 Eth
3 Prop
4 But
5 Pent
6 Hex
7 Hept
8 Oct
9 Non
10 Dec
20 Icos
30 Tricos
For branched chain hydrocarbons
First of all, a perent chain is decided that is the longest carbon chain of the molecule. It
should contain the max. no. of carbon atoms amongst all chains. e.g. I is the correct way of
numbering, not II.

H2
C

H
C

H3C

H2
C

H2
C

H2
C

H
C

CH3

H2
C

CH3

CH2CH3

H3C

H
C

H2
C

H2
C

H2
C

CH3

H
C

H2
C

H2
C

CH3

CH2CH3

7 8
II
If there are two/more chains of same no. of carbon atoms, then chain with max. no. of
sustituent/branches is considered the parent chain.
The numbering is done in such a way that the branches get the lowest possible numbers.
These branches or small chains are called alkyl groups. The names of these groups are written
as prefix. An alkyl group is the alkane minus one hydrogen atom and it is named by
substituting ane of alkane by yl. e.g CH3 Methyl, -CH2CH3 Ethyl etc.
These substituents can be branched also and these are named as trivial names. E.g.
H
C

H3C

H
C

H3CH2C

CH3

CH3

sec-butyl

Isopropyl

C
CH3

tert-butyl

H
C

H2
C

CH3

Isobutyl

CH3

CH3
H3C

H3C

H3C

H2
C

CH3

Neopentyl

If the same alkyl group occurs more than once as a side chain, we indicate this by the prefix
di-, tri-, tetra-, etc., to show how many of these alkyl groups there are, and indicate by various
numbers the positions of each group. Ex- 2,2,4-trimethylpentane.

Carbon atom of the branch that attaches to the parent chain is numbered 1.
Example:
CH2CH3
H2
C

H3C

H2
C

10

H2
C

H2
C

H
C

H2
C

C
2H

4 CH2
H3C

CH3

H2C

CH3

5-(2-Ethylbutyl)-3,3-dimethyldecane

CH3
H3C

C
H

H2C
H2
C

C
H

CH3
H2
C

CH3

4-Ethyl-2-methylhexane

10

H2
C

CH3

COMBUSTION METHOD
The percentage of carbon and hydrogen is determined by burning the organic compound in
excess of oxygen and in presence of CuO. Carbon is oxidised to CO2 and hydrogen to water.
CxHy

xCO2 + (y/2) H2O

+ (x+y/4) O2

Mass of water is determined by passing it over anhydrous calcium chloride and that of carbon
dioxide by passing over conc. Solution of KOH. Increase in their respective masses gives the
amount of water and CO2 and from which, we calculate percentage of carbon and hydrogen.
Let the mass of the org. Compound is m g and mass of water and carbon dioxide be
m1 and m2 g respectively;
12 x m2 x 100
Percentage of carbon =
44 x m

Percentage of hydrgen =

2 x m1 x 100
18 x m

11

12

ISOMERISM

Existence of one molecule in different forms, molecular formula remaining same.

STRUCTURAL/CONSTITUTIONAL
(overall structural change)
STEREO
(space orientation change)

ISOMERISM

CONFORMATIONAL
(due to rotation around C-C)

STRUCTURAL
ISOMERISM

Chain

Position

Functional
Group

Metamerism

Tautomerism
C

hain Isomerism

It arises due to variation in chain length, total no. Of carbons remaining the same. It is
shown by only acyclic compounds. Methane, Ethane and Propane do not show Chain
isomerism. Butane shows two chain isomers, normal Butane and iso-butane (IUPAC
Name is 2-methylpropane.
CH3-CH-CH3
CH3-CH2-CH2-CH3
n-butane

CH3

iso-butane

Effects of chain isomerism

The branched isomer has lesser boiling point than unbranched isomer. We can say that the
more the branching, lesser is the boiling point. Because surface area decreases with

branching and hence the Van der Waals force of attraction.

But in case of melting point, the case is just opposite. More is the branching, more is the
melting point. Because symmetry increases with branching and hence the melting point.

13

Melting point
increases

Boiling point
increases

More the branching, lesser the dipole moment.

Problem: Four organic compounds having dipole moment in debye are A: 0.03, B: 0.7, C:
1.1, D: .001. Arrange them in the decreasing order of melting points.
Ans: D > A > B > C
Melting point is directly related to branching and dipole moment is lowest for the most
symmetrical structure. So, the one with lowest dipole moment will have the highest melting
point and so on.
Note: Order will be opposite in case of boiling point.

Position Isomerism
Due to change in position of functional group along the same carbon chain.
CH3-CH2-CH2-Cl
CH3-CH-CH3
Cl
Chain and position isomerism cannot take place together. If there is confusion of an

isomer being a chain or position isomer, assign it as Chain. e.g. Below given isomers
are chain isomers. First one will be called Butane nitrile and second one will be called
2-propane nitrile.
CH3-CH2-CH2-CN

CH3-CH-CH3

CN

Principal functional groups like CHO, -COOH, -CN, -NC, -COCl, -COOR, -CONH2,
-SO3H will always be at first position while considering isomerism.

Mono-substituted cyclic compounds do not show position isomerism. E.g.

Cl

Cl

14

Problem: Two compounds both containing OH group and having molecular formula C 7H8O
are given. One gives violet-red coloration with Ferric Chloride solution but the other does
not. Identify both of them.
Ans: A phenol gives red violet colour with ferric chloride. One which does not give positive

CH3

CH2OH

OH

Ferric Chloride test is

and the one which gives is ortho/meta/para

.
Functional group isomerism
In chain & position isomerism, only physical properties of molecules change whereas

chemical properties usually remain same.

Chain in Functional group- Functional group isomerism.

e.g. Alcohols & ethers
Mol. Formula C2H6O can be CH3CH2OH or CH3OCH3
Problem: Two isomers (mol. Formula C2H6O), one has a boiling point of 78oC, gives positive
Ceric ammonium nitrate test and gives hydrogen gas on reaction with sodium metal while the
other has boiling point 11oC and does not react with Ceric ammonium nitrate or sodium
metal.
Ans: The first isomer is ethyl alcohol (ethanol) CH3CH2OH and the second is dimethyl ether
(ethoxy ethane) CH3OCH3.

Ring-chain isomerism:- special case of functional group isomerism.

e.g. CH3CH=CH2 and

are also functional group isomers.

Metamerism
Change in no. Of carbon atoms along divalent O, trivalent N and oxo group.

, C=O

e.g. CH3CH2OCH2CH3 and CH3OCH2CH2CH3

Metamerism is special case of position isomerism.

Tautomerism

Arises due to migration of acidic hydrogen from less electronegative carbon to more
electronegative oxygen or nitrogen. E.g. keto-enol tautomerism

H2
C

CH3
C
O
keto form

15

CH3
C
CH2
enol form
H

keto form is stabler. Equilibrium lies to backward.

Tautomerism is a dynamic chemical equilibrium. We can apply Le Chatelier Principle.

Both different forms are called tautomers of each other. They exist as equilibrium

mixture whose composition is fixed.

It is not a physical isomerism like other structural isomers.
As tautomerism is a chemical process, laws of chemical kinetics can be applied to it

and rate constant can be calculated for tautomeric change.

Tautomerism is catalysed by acid or base.

Rate of tautomerism is higher in solvent which acts as both acid and base
We can say that tautomerism is special case of functional group isomerism.
Keto-enol tautomerism
STEREOISOMERISM

OPTICAL
ISOMERISM

GEOMETRICAL
ISOMERISM

ENANTIO-

DIASTEREO

MERISM

MERISM

Stereoisomers (stereomers) have the same bonding order of atoms but differ in the way
these atoms are arranged in space. They are classified by their symmetry properties in terms
of certain symmetry elements. The two most important elements are as follows:
1. A symmetry plane divides a molecule into equivalent halves. It is like a mirror placed so
that half the molecule is a mirror image of the other half.

16

2. A center (point) of symmetry is a point in the center of a molecule to which a line can be
drawn from any atom such that, when extended an equal distance past the center, the line
meets another atom of the same kind.

A chiral stereoisomer is not superimposable on its mirror image. It does not possess a plane
or center of symmetry. The nonsuperimposable mirror images are called enantiomers. A
mixture of equal numbers of molecules of each enantiomer is a racemic form (racemate).
The conversion of an enantiomer into a racemic form is called racemization. Resolution is
the separation of a racemic form into individual enantiomers.
Chirality:- sp3 hybridised carbon having 4 different groups attached. A chiral carbon has the
ability to rotate plane polarised light. Plane ploarised light is light vibrating in one plane.

e.g.

CH3
Cl C H
F
The blue

carbon is chiral carbon.

CH3
H C Cl
F

CH3
Cl C H
F

Non-superimposible
mirror images

17

The molecule which rotates plane-polarised light to the right is called dextrorotatory.
Similarly, the one which rotates to the left is called leavorotatory.
Stereomers which are not mirror images are called diastereomers. Molecules with a plane or
center of symmetry have superimposable mirror images; they are achiral.
The specific rotation []T is an inherent physical property of an enantiomer which, varies
with the solvent used, temperature (T in C), and wavelength of light used ().
It is defined as the observed rotation per unit length of light path, per unit concentration (for
a solution) or density (for a pure liquid) of the enantiomer;

-observed rotation, in degrees

l - length of path, in decimeters (dm)
c -concentration or density, in g/mL_kg/dm3
and where, by convention, the unit degdm2/kg of []T is simply written degrees ().
is an additive/extensive property.
Problem: How could it be decided whether an observed dextrorotation of +60 is not actually
a levorotation of -300?
Ans: By halving the concentration or the tube length. That would halve the number of
optically active molecules, and the new rotation would be +30 if the substance was
dextrorotatory or -150 if it is levorotatory.
If one chiral centre is present then the molecule is always optically active.
18

COOH
H C Cl
F

COOH
Cl C H
F

Non-superimposible
mirror images

Two optical isomers

If more than one chiral centre is present then the molecule may or may not be optically
active. The compounds which are optically inactive in such cases are called meso
compounds.
Case I: Compound containing n chiral carbons in which first and last carbons are
asymmetrically substituted.
Total no. Of optically active forms = 2n
No. Of enantiomeric pairs= 2n/2
No. Of meso compounds = 0
Case II: Compound containing n chiral carbons in which first and last carbons are
asymmetrically substituted.
Case II a: n=even
CHO
H
HO

OH
H
CH2OH

Total no. Of optically active forms = 2n-1

19

No. Of enantiomeric pairs= 2n-1/2

No. Of meso compounds = 2(n/2)-1

Case II b: n=odd
Total no. Of optically active forms = 2n-1- 2(n-1/2)
Total no. Of optically active forms = [ 2n-1- 2(n-1/2)] /2
No. Of enantiomeric pairs= 2n-1/2
No. Of meso compounds = 2(n-1/2)
Problem: optical activity disappears when (R)-2-chlorobutane is allowed to stand in aqueous
H2SO4 and when (S)-2-iodooctane is treated with aqueous KI solution.
Ans: Optically active compounds become inactive if they lose their chirality because the
chiral center no longer has four different groups, or if they undergo racemization. In the two
reactions given, C remains chiral, and it must be concluded that in both reactions,
racemization has occured.
DIASTEREOMERS: They are configurational isomers not related as mirror images.
Their properties are different.

20

For all practical purposes, they are two different compounds and they can be separated by any
conventional method of separation. E.g.
CHO

CHO
H
HO

OH

HO

HO

H
CH2OH

CH2OH

DIASTEREOMERS
Geometrical isomerism/Cis-Trans isomerism
Due to restricted rotation around C=C, C=N and cyclic compounds.
a

a
C

Cis-same group along the same plane b

b
C

Trans- same group across the diagonal b

The C atom around which restricted rotation is present, must have asymmetric substitution.
a

a
C

e.g. b

a
C

C
b

x
C

C
b

21

CH3

H3C
y

a
C

Molecules like b

a
C

C
H3C

CH3

will not show geometrical isomerism.

Syn-Anti isomerism
In case of oximes, lone pair of electrons is also counted in isomerism. A lone pair is given the
least priority in Cann-Ingold-Prelog system of nomenclature. E.g.
R2

R1

R1

R2
C

OH

OH

anti

syn

R1 has higher priority compared

to R2 and OH has higher priority
than lone pair.In case of syn, both
the higher priority groups are on the
same side and in anti, they are
opposite.

Properties of Cis and trans isomer

(1.)Boiling point of cis isomer is higher than that of trans while melting point of trans
isomer is higher than that of cis.
H3C

CH3
C

H3C

H
C

Surface area high

boiling point high

C
CH3

symmetry high
melting point high
22

(2.) Trans isomer is stabler than cis because of lesser repulsion.

(3.) Dipole moment of cis isomer is always higher than trans isomer. Dipole moment of
trans isomer is zero if the compound is of the type abC=Cba because it gets cancelled
out.
E.g. a) 1,1-dichloroethylene, (b) cis- and trans-1,2-dichloroethylene.

(4.)Both cis and trans isomers are two different compounds for all practical purposes.
CONFORMATIONAL ISOMERS
Due to rotation around C-C
Any compound having more than one carbon atom may be represented as conformations.
Hb

Ha

Ha

2
C
Hb

Dihederal angle: Angle between two planes that contain atoms Ha and Hb is called
dihederal/torsional angle (.

The values of for the closest pairs of C-H bonds in the eclipsed and staggered
conformations are 0 and 60, respectively. There are an infinite number of
conformations with energies between staggered and eclipsed conformations. All
intermediate conformations are called skew; their values lie between 0 and 60. For

23

simplicity, we are concerned only with conformations at minimum and maximum

energies.

Newmann Projection of conformations of ethane

H
H
H

Eclipsed

H Ha

Ha

Hb Ha

Hb

H
H

Staggered
(Most stable)

Eclipsed

Newmann Projection of conformations of n-butane

24

Hb
H

Staggered form is always more stable than eclipsed form in any case. So, its
percentage will be more in any mixture.

Problem: 1,2-Dibromoethane has a zero dipole moment, whereas ethylene glycol,

CH2OHCH2OH, has a measurable dipole moment.
Ans: 1,2-Dibromoethane exists in the anti form, so that the C-Br dipoles cancel and the net
dipole moment is zero. When the glycol exists in the gauche form, intramolecular H-bonding
occurs. Intramolecular H-bonding is a stabilizing effect which does not occur in the anti
conformer.

Hydrogen bonding
25

The origin of hydrogen bonding

The molecules which have this extra bonding are:

Note: The solid line represents a bond in the plane of the screen

going back into the screen or paper away from us, and wedge-sh
towards us.

Each of these molecules:

The hydrogen is attached directly to one of the most

electronegative elements, causing the hydrogen to acquire a significant

amount of positive charge.

Each of the elements to which the hydrogen is attached is not only

significantly negative, but also has at least one "active" lone pair.
Lone pairs at the 2-level have the electrons contained in a relatively small
volume of space which therefore has a high density of negative charge.
Lone pairs at higher levels are more diffuse and not so attractive to
positive things.
A hydrogen bond is the electrostatic attraction between an atom of
hydrogen and a second, electronegative atom--whether structurally the
two are part of the same molecule or are of different molecules. If bonding
occurs between different molecules, it is intermolecular. If it occurs within
one molecule, it is intramolecular. The length of a chemical bond indicates
26

its strength. The stronger it is, the shorter it is. Hydrogen bonds are shorter
than van der Waals bonds, but longer than covalent and ionic bonds.
Intermolecular Hydrogen Bonding
The outstanding example of hydrogen bonding is water. One hydrogen
atom of one water molecule forms a weak bond with one oxygen atom of
another water molecule. The other hydrogen atom of the first water
molecule can form a bond with the oxygen of a third water molecule.
Interestingly, under the special conditions of freezing and pressurization,
all hydrogen to oxygen bonds in water can be made to approach equality.
This is called symmetric hydrogen bonds, in which each bond possesses a
measure of covalent character.
Intramolecular Hydrogen Bonding
An example of an intramolecularly bonded species is 2-cyanoethanol,
HO-CH2CH2-CN. In this instance, the hydroxyl hydrogen (the H of the
HO- group) is electrostatically drawn to the nitrogen of the cyano group
(the N of the -CN group). The resultant structure is a loosely flexible sixmember ring--a hexagon--with the skeleton H-O-C-C-C-N. The other
hydrogen atoms are attached to the two, central, carbon atoms.
Intramolecular bonding can position atoms to favor certain reactions over
others.
General Effects of Hydrogen Bonding
Since intermolecular hydrogen bonding draws molecules closer together,
liquids experience an increase in density. It requires energy to disrupt
27

these bonds, so hydrogen-bonded liquids experience a higher boiling

point. Molecular shapes in the liquid state are affected as is the crystal
lattice of solids, because hydrogen bonds, although flexible, distort
molecules into specific positions. Water-solubility is increased for
hydrogen-bonded compounds, since water can establish hydrogen bonds
with dissolved solute.
Polymer and Macromolecule Effects of Hydrogen Bonding
In biologically active macromolecules, hydrogen bonding contributes to
higher levels of structure, including protein folding. Hydrogen bonding is
largely responsible for the double helix of DNA. Parallel hydrogen
bonding (hydrogen bonding between two linear structures) add strength to
fibers such as cellulose.

Basis of Organic Reactions

An Intermediate is a short-lived species formed during the course of a reaction.

It is formed in case of multi-step reaction.

It may be charged or neutral.

If it is charged, it gets stabilised in polar solvent.

If it is neutral then it gets stabilised in non-polar solvent.

28

Charged Intermediates

Neutral Intermediates

Carbocation

Free radical

Carbanion

Carbene
Nitrene
Benzyne

Polar effect: Polar effect is the displacement of electron in a covalent bond. This
displacement may be temporary or permanent.

POLAR EFFECT
PERMENENT

TEMPORARY
ELECTROMERIC EFFECT

INDUCTIVE EFFECT

MESOMERIC EFFECT

HYPERCONJUGATION

INDUCTIVE or I EFFECT: Relatively permanent displacement of electron towards

electronegative atom in a sigma bonded molecule. It induces permanent dipole moment in a
molecule.
Reactivity may be decided by other factors but possibility of a reaction is mostly decided by I
effect.

29

It is of two types:
(1.)+ Inductive (+I) effect: Electron releasing effect
(2.)- Inductive (-I) effect: Electron withdrawing effect
+I effect: Electron releasing effect. Alkyl groups show this effect.

H3C

It plays an important role in determining the basic strength of a molecule. According to Lewis
concept, a base is a species which can donate a pair of electrons. +I effect increases the
electron density and enhances the basic strength. But Steric hindrance is a more important
factor in determining the basic strength.
e.g. in case of amines, the order of the basic strength is
2o Amine > 3o Amine > 1o Amine > NH3
If only +I effect is taken into consideration then 3 o amine should have the highest basic
strength because it has three electron releasing alkyl groups but the three alkyl groups also
hinder the electron donation.
Electron donating groups decrease acidity.

-I effect: Electron withdrawing effect. It is shown by a large no. of electronegative atoms or

groups. E.g.-

30

-NR3 , -NH3 , -NO2 , -CN , SO3H , -NR2 , -NH2 , -OH , -OR , -COOR, -COOH, -COCl , -CONH2

O
C

R
C

, -CHO, -C-R , -F , -Br, -I, -Ph

O

-I effect depends upon

(1.) Oxidation state: Increases with increase in oxidation state.
e.g. NO2

will have greater I effect than NH2.

O.N. of N=+5

O.N. of N= -2

(2.) s character : Increases with increase in s character. E.g.

H
C N will have greater -I effect than
C NH .
50% s
33.3 % s
character
character

(3.) Electronegativity : Increases with increase in electronegativity.

e.g. F > -Cl > -Br > -I
-OH will have greater inductive effect than -OR because +I effect of R (release of electrons)
will lower the I effect.

Acidic Strength & -I effect

-I effect increases the acidic strength as the groups which withdraw electrons can
stabilise the negative charge on the conjugate base. (Smaller the pK a value, stronger is
the acid/ larger the Ka value, stronger is the acid).

e.g. Order of acid strength

31

O
F

>

OH
2-Fluoroacetic acid

O
Cl

>

OH
2-Chloroacetic acid

O
Br

OH
2-Bromoacetic acid

>

O
I

OH
2-Iodoacetic acid

Both the inductive effects are distance dependent effect i.e, they decrease with
increasing distance.

MESOMERIC/RESONANCE EFFECT

Displacement of electrons in bonded compound.

This effect operates through bond, + charge, - charge, lone pair of electrons and odd
electrons present at alternate position.

32

Extension of resonance via - bond, + charge, - charge, lone pair of electrons etc. Is
called conjugation.
Role & Importance of resonance effect

It reduces the bond length of single bond. For a molecule with alternate single and
double bond, all the bond lengths are found to be equal.
Aromaticity
Acidic and basic character

Acidity of a compound is decided by the stability of its conjugate base. Delocalization of

negative charge after the removal of H+ stabilizes a conjugate base. More stabilized a
conjugate base, stronger is the acid.

Comparing the acidities of HClO, HClO2, HClO3, and HClO4. They have pKa values 7.5,
2, 1, and about 10, respectively. In each case the acidic proton is on an oxygen
attached to chlorine, that is, we are removing a proton from the same environment in
each case. Then, why is the difference? Once the proton is removed, we end up with a
negative charge on oxygen. For hypochlorous acid, this is localized on the one oxygen.
With each successive oxygen, the charge can be more delocalized, and this makes the
anion more stable. For example, with perchloric acid, the negative charge can be
delocalized over all four oxygen atoms.
B:
H

Cl

Cl

Cl

O
O

33

O
Cl
O

Acidity of ethanol (pKa = 15.9), acetic acid (pKa = 4.8) and methane sulphonic acid (pKa
= -1.9).

In ethoxide, the negative charge is localized on one oxygen atom, whilst in acetate the charge
is delocalized over two oxygens and in methane sulfonate, it is spread over three oxygens.

pKa of cyclohexanol is 16 while that of phenol is 10.

Similarly, Aniline is a weaker base than Cyclohexylamine. In case of cyclohexylamine,

lone pair is localised (easily available for donation) and in aniline, the lone pair is in
partial delocalisation with the ring (partial because the plane of the lone pair is 40 o away
from the plane of the ring).
NH2

NH2

34

Amides are weaker bases than amines. No protonation can occur on nitrogen of amides.
In case of amides, Nitrogen is sp 2 hybridised with lone pair in the p orbital having good
overlap with the carbonyl group. This delocalisation binds the lone pair.
O
R

O
N
R

N
R

Note: Mesomeric effect is always dominating than inductive effect and it is always the
deciding factor if both effects are present.
e.g. In case of Haloarenes

Problem: Arrange the following in order of decreasing acid strength.

Water, ethanol, phenol
Ans: Phenol > water > ethanol
Phenoxide ion is stabilized by resonance. RO - is destabilized because of electron
releasing effect of alkyl group.
Note: In a reaction of alcohol and water, water acts as proton donor.

O +

Base

Acid

Conjugate
acid

OH

Conjugate
base

Sodium ethoxide is a stronger base than Sodium hydroxide due to the similar reason. (RO- is a
stronger base than OH-.)

Hyperconjugation

35

Delocalisation of electrons.

Separated proton always remains closer to the molecule. It is also called No bond
resonance because at least in one canonical form, it is separated from the molecule.

It is also called Second order resonance due to migration of electrons.

No. Of hyperconjugated forms = n, where n is the no. Of hydrogens

Effects

To decide the stability of unconjugated alkene.

More the no. Of hyperconjugated structures, more is the stability of the molecule.

If the no. Of hyperconjugated structure is same then more symmetrical structure will be
more stable.

Hyperconjugation decides the stability of alkyl carbocation in the same way, more the
no. Of hyperconjugated structures, more is the stability of the carbocation.

Hyperconjugation effect is a weak effect than mesomeric effect because of breaking of

C-H bond but stronger than inductive effect because it is the actual delocalisation of
electrons.
Carbocations
36

A carbocation is a trivalent positively charged sp2 hybrid planar carbon having vacant p
orbital( perpendicular to the plane of the carbocation). It is diamagnetic and a Lewis acid.
R1

R2

R3

Planar

Methods of formation
1.) By breaking of C-X bond as in first step of SN1 reaction.

R3C

CR3 + X

X = Cl, Br, I

2.) Dehydroxylation of alcohols

R3 C

OH

+H

R3C

CR3 + H2O

OH2

3.) Protonation of alkenes

+H

Factors of stability
A carbocation is a charged particle. So, it is more stabilised in a polar solvent.
As it is a charged intermediate. So, any factor that decreases positive charge or delocalises the
charge will stabilise and these factors are
1.) I effect: + I effect increase the stability while I effect decreases it

37

2.)

Hyperconjugation: More the no. Of hyperconjugated structures, more is the stability of

the carbocation.

3.)

Mesomerism

4.)

Aromaticity: Whenever during the formation of a carbocation, an aromatic structure is

achieved then this carbocation becomes most stable carbocation.

5.)

S character: Higher the s character of the carbon atom on which the

+ charge is present, lower will be the stability of carbocation.
CARBANION

Negatively charged trivalent carbon.

Either planar (sp2) or pyramidal (sp).

Carbanions with bulky alkyl groups are sp2 hybridised.

They are important intermediate in several types of condensation reactions like Aldol
condensation. Carbonyl chemistry is governed mainly by carbanion formation. It acts as
a nucleophile. There are so many examples of nucleophilic addition reaction.

Methods of preparation

Using a strong base to abstract H+ .

38

Factors of stability
As it is a charged particle, it is more stabilised in polar solvent than non-polar solvent. Order
of stability in
Polar protic solvent > polar aprotic solvent > non-polar
Inductive effect: - I effect increases stability while + I effect decreases it.
S character: Greater the s character, greater is the stability.
Aromaticity
Free Radical Intermediate
It is trivalent, planar (sp2) paramagnetic and free from any charge (neutral) formed by
homolytic cleavage of a covalent bond.

Homolytic

fission

+ B

Stability is just like stability of carbocations except the solvent factor.

CH3 < 1o < 2o < 3o
They are more stable in non-polar solvent. Unlike carbocation and carbanion, solvents do not
affect the reaction of free radicals.
39

Free radical reactions take place in presence of peroxide or very high temperature or UV
radiation.
Formation of free radical takes place by homolytic fission of the bond.

A B

Homolysis

A + B

Halogenation of alkanes
This is an example of free radical substitution reaction. It takes place in the presence of
diffused sunlight or UV light.
Mechanism:
1.) Initiation: Breaking of Cl-Cl bond to generate chlorine free radical

Cl
2.)

Cl

Cl

+ Cl

Propagation: Chlorine free radical attacks on methane to generate methyl free radical
and then methyl again attacks on chlorine to generate chlorine free radical. The process
gets repeated.

The first propagation step i.e, the attack of chlorine free radical on methane to generate
methyl free radical is the rate determining step.
The overall reaction is the sum of above two propagation steps.

40

3.)

Termination occurs via following reactions.

Carbene
Divalent neutral carbon is called as carbene. With six electrons in valence shell (incomplete
octet), they are electron deficient. They are of two types, singlet and triplet. Singlet is sp 2
(angular), diamagnetic, electrophilic, less stable, less reactive and triplet is sp (linear),
paramagnetic, biradical, more stable, more reactive.

Triplet carbene

Singlet Carbene

Generation of carbene:
From Chloroform (CHCl3) Using a strong base: As in Reimer-Tiemann and Carbyl amine
reactions.
Reimer-Tiemann reaction

41

OH

OH

OH

CHO

CHCl3, NaOH

Heat

CHO

Carbyl amine reactions.

Generation of carbene:

Cl

Cl

OH

Cl

H2 O

Heat

Cl

Cl
C

Cl

Cl

Cl

ALKANES
Organic compounds having only two elements, carbon and hydrogen are called hydrocarbons.
They are divided into two main classes, aliphatic and aromatic.

The Alkane family

General formula: CnH2n+2
First member is Methane (CH4)
Also known as Marsh gas, chief constituent of natural gas (~97%)
42

H
H

Hybridisation sp3
Structure: tetrahederal
Bond angle: 109.5o
Intermolecular force of attraction: van der waal type
Preperation of alkanes
1.)

Hydogenation of alkenes:
CnH2n

H2+ Pt/Pd/Ni

CnH2n+2

2.) From alkyl halides

a.) Wurtz reaction (for symmetrical alkanes)
When only one alkyl halide is taken
Dry ether
RX + 2Na + XR
R
R + 2NaX
When two different types of alkyl halides are taken then we get a mixture of products.
Dry ether
R' + 2NaX
R' + R'
R
R + R
RX + 2Na + XR'
This is because the two alky halides not only react with each other but with themselves as
well. So, we cannot prepare an alkane with odd no. of carbon atoms by this method.
b.) Reduction of alkyl halides
i)
Using Zn and HCl.
Zn/HCl
RH + HX
RX + H2
ii)
iii)

With hydrogen in presence of transition metal catalyst

Pd or Pt
RH + HX
RX + H2
With HI and red phosphorus
RBr + HI

iv)

Red P
423 K

RH

By Zn-Cu and alcohol

43

+ HBr + HI

Zn2+ + 2e_

Zn
RX + e-

X- + R

R + e-

RRH + C2H5O-

R- + C2H5OH
c.)

Using Grignard reagent

RH + Mg(OH)X
RMgX +
HOH
Alkyl magnesium Water
Alkane
halide
Thats why Grignard reagent is always protected from moisture because it is very reactive

and immediately gets converted to alkane.

In Place of RMgX, RLi can also be used.
d.) Using Lithiumdialkylcuprate (Corey-House synthesis)
1.Li
CH3CH2CH2CH3
(CH3CH2)2CuLi + C2H5X
CH3CH2X
2. CuI
3.) From carboxylic acids
a.) Decarboxylation reaction
CaO
RH + Na2 CO3
RCOONa + NaOH
Heat
Sodium salt
of carboxylic acid
A molecule of CO2 is removed from carboxylic acid. Thats why this reaction is called
decarboxylation reaction.
CaO keeps NaOH dry because NaOH is hygroscopic (absorbs moisture).
b.) Kolbes electrolysis (gives symmetrical alkane): An aq. Solution of sodium/potassium
salt of a carboxylic acid is electrolysed to give alkane at anode.
Electrolysis
R-R + 2 CO2 + H2 + 2KOH
2RCOOK + 2H2O
2 CH3COOK (aq.)
At anode:

Electrolysis

2 CH3COO- + 2K+

2 CH3COO- - 2e-

2 CH3COO

2 CH3COO

CH3CH3 + 2CO2

H+ + e-

At cathode:

H + H
c.)

H2

By reduction with HI
CH3COOH + 6HI

reduction

CH3CH3 + 2H2O + 3I2

Physical properties of alkanes

44

1.)

Non-polar molecules which are held by weak Van der Waals forces of attraction. These
forces depend upon size (surface area) of the molecule. C 1-C4 are gases, C5 C17 are

2.)

liquids and rest are solids.

They have low boiling points which inc. With inc. In chain length. Boiling point

3.)

decreases with branching.

Melting point of alkanes with even number of carbon atoms is higher than that of next
alkane with odd no. of carbon because melting point is a symmetry dependent property.

4.)
5.)

even
odd
They are soluble in non-polar solvents like ether, benzene etc.
Alkanes are ligher than water. Their density increases With increases in no. of carbon

atoms.
Chemical properties of alkanes
As they are saturated hydrocarbons, they are very less reactive and inert but they undergo
some substitution reactions.
1.) Halogenation: Replacement of one/more hydrogen by halogen atoms. (Details of
mechanism have been discussed in free radical chemistry.)
Light or heat
CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl
CH4 + Cl2
Bromination is less rapid than chlorination.
Iodination requires the presence of an oxidizing agent because HI reverses this reaction.
In more complex alkanes, the abstraction of each different kind of H atom gives a different
isomeric product 1o, 2o, 3o.
Three factors determine the relative yields of the isomeric product:
(1) Probability factor. This factor is based on the number of each kind of H atom in the
molecule. For example, in CH3CH2CH2CH3, there are six equivalent 1 Hs and four
equivalent 2 Hs. The odds on abstracting a 1 H are thus 6 to 4, or 3 to 2.
(2) Reactivity of H.: The order of reactivity of H is 3 > 2 > 1.
(3) Reactivity of X.: The more reactive Cl. is less selective and more influenced by the
probability factor. The less reactive Br. is more selective and less influenced by the

45

probability factor. According to the reactivity-selectivity principle, if the attacking

species is more reactive, it will be less selective, and the yields will be closer to those
expected from the probability factor.
2.)

Combustion:
In absence of air, they undergo pyrolytic cracking.

In presence of air, alkanes are oxidized to carbon dioxide and water with evolution of large
amount of heat. That is why they are used as fuels.

3.)

Controlled oxidation: On heating with regulated supply of air at high pressure and in
presence of suitable catalyst, alkanes give variety of products depending upon the
condition.
CH4 + O2
CH4 + O2

Cu/523K/100 atm
Mo2O3, Heat

2CH3CHO
HCHO

(CH3COO)2Mn
2CH3CH3 + 3O2
2CH3COOH + 2H2O
Tertiary alkanes can be oxidised to corresponding alcohols using KMnO4.
OH

CH3

KMnO4

H3C
CH3

4.)

H3C

CH3
CH3

Isomerisation: n-Alkanes on heating with anhyd. Aluminium chloride in presence of

HCl isomerise to branched chain isomers.

C6H14

5.)

Anhyd. AlCl3/HCl

Aromatization/reforming: n-alkanes having 6 or more carbons on heating at high

temperature and pressure of 10-20 atm in presence of transition metal oxides get
cyclised.

46

C6H14

6.)

Mo2O3 or V2O5 or Cr2O3

773 K, 10-20 atm

Methane reacts with steam at 1273 K in presence of Ni to give CO and H2.
Ni, Heat
CH4

CO + 3H2

ALKENES
Unsaturated hydrocarbons containing C=C having general formula C nH2n. They are also
known as Olefins.
Nomenclature
i)
The longest continuous chain should include both the carbon atoms of the double bond
ii)

The suffix used for double bond is ene.

iii)

The chain is numbered from the end which gives lower no. to the first carbon
containing double bond.
1 2 3 4 5
CH3CH=CHCHCH3
CH3
4-Methylpent-2-ene

iv)

If there are two or more double bonds, it is named as adiene or atriene.

CH2=CHCH=CH2
Buta-1,3-diene

Isomerism
Alkanes show chain and position isomerism.
i)

Chain Isomerism: Alkenes higher than ethane and propene show this isomerism.
3 2 1
CH3C=CH2

1
2 3 4
CH2=CHCH2CH3
Buta-1,3-diene

CH3
2-methylprop-1-ene
47

ii)

Position isomerism: These isomers differ in position of double bond.

CH2=CHCH2CH3

CH2CH=CHCH3
But-2-ene

iii)

But-1-ene

Geometrical isomerism: discussed in isomerism section

Preperation of alkenes

1.)

From alkyl halides: Dehydrohalogenation

RCH2CH2X

Alc. KOH
Heat

RHC=CH2 + HX

This reaction is elimination reaction.

Ease of dehydrohalogenetion
Iodine > bromine > chlorine
Tertiary > Secondary > Primary
Saytzeff rule: In case of dehydrohalogenation, that alkene is the preferred product which has
more no. of alkyl groups attached to the double bonded carbon atom.
CH3
H3C

C
H

C
H

CH3

major product

CH3
H3C

H
C

Alc. KOH
CH3
CH3

Br

2-bromo-3-methylbutane
H3C

C
H

C
H

minor product

48

CH2

2.)

From dihalogen derivative (Vicinal dihalides)

CH2Br
CH2Br

3.)

Heat
Ethanol

CH2=CH2 + ZnBr2

From alkynes: Pd-C, H2 (Lindlars catalyst) gives Cis alkene while Na/liquid

Ammonia (Birch reduction) gives Trans alkene.

Lindlar's

H3C
C

catalyst
H
H3C

CH3
C
H

CIS

CH3
H3C

Na-NH3

H
C

CH3

TRANS
4.)

From alcohols: Dehydration of alcohols (ellimnation reaction)

CH3CH2OH

H2SO4/ H3PO4
443 K

CH2CH2 + H2O

Problem: Dehydration of: (a) CH3CH2CH2CH2OH yields mainly CH3CH=CHCH3 rather than
CH3CH2CH=CH2, (b) (CH3)3CCHOHCH3 yields mainly (CH3)2C=C(CH3)2.
Ans: (a) The carbocation (R+) formed in this reaction is 1 and rearranges to a more stable 2
R2CH+ by a hydride shift (indicates as ~H:; the H migrates with its bonding pair of
electrons).

49

(b) The 2 R2CH+ formed undergoes a methide shift (~:CH3) to the more stable 3 R3C+.

5.)

By electrolysis of Sodium/potassium salts of dicarboxylic acids (Kolbes reaction)

CH2COOK

2H2O

Electrolysis

H2C

CH2 + 2CO2 + H2 + KOH

CH2COOK

Physical Properties
First 4 members are gases. C 5-C18 are liquids and higher members are solids. They are
colourless and odourless.
Melting points of alkenes are higher than alkanes because p electrons of double bond are
polarizable. As a result, intermolecular forces of attraction are stronger. M.P. & B.P. inc. With
inc. In the molecular mass but they do not show any regular trend. Trans-alkenes have higher
m.p and lower b.p. than Cis-alkenes.

m.p. = 167.4 K
b.p. = 274 K

m.p. = 134.2 K
b.p. = 277 k

50

Dipole moments: Alkenes are weakly polar because p-electrons of double bomds are easily
polarisable. So, their dipole moments are higher compared to alkanes.
(More is discussed in geometrical isomerism.)
They are soluble in non-polar solvents.
Chemical Properties
As they have bond present in them, they are quite reactive compared to alkanes because
electrons are weakly held and more exposed. They have a tendency to undergo electrophilic
addition reaction.

A B

The electrophilic addition takes place in 2 steps via the formation of carbocation
intermediate.
step1:

Br

H
H

H + Br

Ethyl carbocation
step 2:
H
H

H + Br

Br

Hydrogenation reaction takes place in presence of transition metal catalyst.

51

The addition reaction between an alkene and water to form an alcohol: This reaction is
called hydration, requires a catalystusually a strong acid, such as sulfuric acid (H2SO4):

Addition of Br2 to alkenes

It takes place via two mechanisms, one is given to explain the formation of cis product and
other to explain trans.
The addition of bromine to Z- or E- 2-pentene:

For an E-alkene

52

Formation of the bromonium ion can occur from either the top or bottom face of the alkene.

These are equivalent, since the molecular plane is a plane of symmetry.

Attack on the left carbon of either bromonium ion gives a product that is the
enantiomer of the product from attack on the right end.

53

Hence the two pathways for attack must have equal energies, and the products must
be formed in equal amounts.

We get the RS and SR enantiomers, but none of either RR or SS. The reaction is
stereoselective.

If reaction occurs on the Z- alkene:

54

the same sequence of events occurs. Since the configuration of one end of the alkene was
opposite, the configuration of one end of the dibromide product is opposite. (Another way to
put it: this alkene is a diastereomer of the E- isomer, so the products must be diastereomers.)

55

We get the RR and SS enantiomers in equal quantities, but none of the RS or SR

diastereomers. The reaction again is stereoselective.
Markovnikov's Rule
This is an empirical rule based on Markovnikov's experimental observations on the
addition of hydrogen halides to alkenes.
The rule states that :
"when an unsymmetrical alkene reacts with a hydrogen halide to give an
alkyl halide, the hydrogen adds to the carbon of the alkene that has the
greater number of hydrogen substituents, and the halogen to the carbon of
the alkene with the fewer number of hydrogen substituents"

The reaction occurs via protonation to give the more stable carbocation:

Here we see that in principle, propene can protonate to give two different carbocations, one
2o and the other 1o.
Formation of the more stable 2o carbocation is preferred.

The carbocation then reacts with the nucleophile to give the alkyl bromide and hence
2-bromopropane is the major product.

56

Although Markovnikov's rule is specifically applied to the addition of hydrogen halides to

alkenes, many additions are also described as Markovnikov or anti-Markovnikov depending
on the regioselectivity of the addition reaction.
Markovnikov's rule can be generaliised" to cover other addition reactions by considering
that the electrophile adds to the least substituted end of the alkene giving rise to the more
stable intermediate. "when an unsymmetrical alkene undergoes addition with E-Nu, then
the electrophile, E, adds to the carbon of the alkene that has the greater number of hydrogen
substituents, and thenucleophile, Nu, to the carbon of the alkene with the fewer number of
hydrogen substituents"
Anti-Markovnikov

Some reactions do not follow Markovnikov's Rule, and anti-Markovnikov products are
isolated. This is a feature for example of radical induced additions of HX and of
Hydroboration.
Radical reactions require an initiation step. In this example, a bromo radical is formed.

57

The reversal of the regiochemistry of addition is the result of the reversal of the order in
which the two components add to the alkene. Radical addition leads to the formation of the
more stable radical, which reacts with HBr to give product and a new bromo radical:

Anti-Markovnikov

Hydroboration-oxidation

Oxymercuration-demercuration

Reaction with halohydrins

58

Diol formation
Via formation of a metallocyclic intermediate,

Ozonolysis

Allylic substitution
The brominating reagent, N-bromosuccinimide (NBS), has proven useful for achieving allylic
or benzylic substitution in CCl4 solution at temperatures below its boiling point (77 C).

59

60

Alkynes
Alkynes are unsaturated hydrocarbons containing carbon-carbon triple bond having general
formula as CnH2n-2. First member is Ethyne C2H2.
Nomenclature
i)

They are named as derivative of corresponding alkanes replacing ane by yne.

ii)

The longest continuous chain should include both the carbon atoms of the triple bond.

iii)

The suffix used for triple bond is yne.

iv)

The chain is numbered from the end which gives lower no. to the first carbon
containing triple bond.

H3C

32

H3CH2CC

CH

H3CHCC

But-1-yne

1
CH

3-Methylbut-1-yne

Just like Alkenes, they show chain and position isomerism.

As they are linear molecules (bond angle 180o), they do not show geometrical isomerism.
Preperation
1.)

By action of water on calcium carbide

CaC2 + 2H2O

2.)

HC

By dehydrohalogenation of vicinal dihalides

61

CH

+ Ca(OH)2

3.)

5.)

alc. KOH

R'

R'

2Zn
Heat

HC

CH

+ NaNH2

HC

CNa

+ CH3Br

EtOEt

RC

CR'

+ ZnBr2

HC

CNa

HC

+ NH3
CH3

+ CH3Br

By electrolysis of aq. Solution of potassium salt of fumaric acid.

+ 2H2O

Electrolysis

CH

+ 2CO2 + H2 + 2KOH

CH

CHCOOK

By dehalogenation of haloform by heating with silver powder.

CHCl3 + 6Ag + Cl3CH

7.)

CR'

Higher alkynes can be prepared by heating sodium salt of acetylene with alkyl halide.

CHCOOK

6.)

RC

By the action of zinc on tetrahalogen derivatives of alkanes

4.)

HC

CH + 6AgCl

Acetylene is prepared by passing hydrogen through electric arc discharge between

Carbon electrodes.

2C + H2

Electric
arc
3270 K

Chemical reactions
62

HC

CH

They are more reactive than alkanes and alkynes due to the presence of two bonds. They
undergo addition and oxidation reactions readily. One important property of alkynes is the
acidic nature of the hydrogen attached to the triple bonded carbon (because hydrogen is
attached to sp hybridised carbon).
1.)

Addition reactions

a.)

Halogenation
Cl
Cl2
HC

CH

HC

CH

Cl2

HC

CCl4

CCl4
Cl

Cl
CH

Cl

Cl

Cl

Cl

Reactivity of halogens: Chlorine > Bromine > Iodine

Iodination stops after one step resulting in trans product.
b.)

Addition of halogen acids

HCl
HC

HC

CH

CH

HCl

HC
H

Cl

H
HBr
H

CH

H3C

HBr
CH2

HC
H

Br

CH
Cl
Br
C
Br

CH3

React

ivity: HI > HCl > HBr

c.)

Addition of hydrogen is stereoselective depending upon the conditions used. (Already

discussed in preparation of alkenes)

63

d.)

Addition of water

e.)

Reaction with Boron hydride

With dialkylacetylenes, the products of hydrolysis and oxidation are cis-alkenes and ketones,
respectively.

f.)

Linear polymerisation
Acetylene/ethylene produces polyacetylene/polyethylene on polymerisation.

64

C
H

H
C

H
C

C
H

g.)

Cyclic polymerisation
On passing through red hot iron tube at 873K, ethylene polymerises to form benzene.
CH
HC

CH

HC

CH

Red hot iron tube

873 K

CH

65