BASIC CONCEPTS IN ORGANIC CHEMISTRY / TYPES OF ORGANIC REACTIONS /

HYBRIDIZATION
HOMOLYTIC AND HETEROLYTIC BOND CLEAVAGES
A covalent bond (σ) between two atoms can undergo fission in two ways:
1. Homolytic fission or Homolysis.
2. Heterolytic fission or Heterolysis.

1. Homolytic fission: In this process symmetrical fission of a covalent bond happens leading to the
formation of free radicals.

A B → A° + B°
e.g. Cl Cl uv light
Cl° + Cl°
or Δ

In this each of the atoms acquire one of the bonding electrons and the products formed
(A˚and B˚) are called free radicals.

“Free radicals are atoms or group of atoms having an unpaired electron.”

Free radicals are electrically neutral and are very reactive because of the tendency of the
unpaired electron to get paired. Hence reactions, which proceed by free radical intermediates, are
very rapid. Homolytic fission is prevalent in gaseous reactions but also occur in other mediums
generating free radical intermediates. Light, heat and catalysts like organic peroxide, azo- compounds
and alkyl nitrates normally initiate Homolysis. The catalysts used for Homolysis are called initiators.

2. Heterolytic fission: In this process unsymmetrical fission of a covalent bond happens leading to the
formation of ions.
A B → A+ + :B–
e.g. H-Br → H+ + Br -

In this one of the atoms acquires both the electrons and thus becoming negatively
charged and the other atom becoming positively charged. Thus ions are produced in Heterolytic
fission.
Heterolytic reactions take place at measurable rates Heterolytic fission occurs readily in i polar
compounds in polar solvents.

REACTION INTERMEDIATES
Heterolytic and homolytic bond fissions result in the formation of short-lived fragments called reaction
intermediates. Among the important reaction intermediates are carbocations, carbanions, and carbon free
radicals.

1. CARBOCATION: (Carbonium ions): Organic ions, which contain positively charged carbon atoms, are
called carbonium ions are carbocations. They are formed by Heterolytic bond fission.

C : Z C+ + : Z-

carbocation
where Z is more electronegative than carbon.

The positively charged carbon atom in a carbonium ion

uses sp2 hybridized orbitals to form three σ bonds. An empty p
orbital extends above and below the plane of the σ bonds. This
empty p orbital makes the carbon atom electron-deficient and
Methyl carbocation
gives it a positive charge. Thus a carbocation will combine with
any substance which donates a pair of electrons (nucleophiles).

The stability of carbocation is influenced by both resonance and inductive effects. For
example, the allyl and benzyl carbocation ions are much more stable than propyl carbocation. Both

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allyl and benzyl carbocation are resonance stabilized but propyl carbocation (CH 3CH2CH2+) has no
resonance forms to stabilize it.

Resonance forms of allyl carbocation:

Resonance forms of benzyl carbonium ion:

Electron releasing groups (+I groups) also stabilise carbocation by partial neutralisation of the
positive charge on carbon.
Thus a tertiary carbocation is more stable than a secondary, which in turn is more stable than
a primary because of the +I effect associated with alkyl groups.

Electron attracting groups (-I groups) will make a carbocation ion less stable.

2. CARBANIONS: Organic ions which contain a negatively charged carbon atom are called
carbanions.They are also formed by Heterolytic fission.

C : Z C: -
+ Z+

carbanion
where Z is less electronegative than carbon.

Filled ‘p’ orbital

(a) (b)

If the negatively charged carbon atom in a carbanion is bonded to hydrogens or alkyl groups it
uses sp3 hybrid orbitals to form three sigma bonds.[structure(a)]

If the negatively charged carbon atom in a carbanion is bonded to an unsaturated group (as in
benzyl carbanion), it uses sp2 hybrid orbitals to form three σ bonds. [Structure (b)]

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The completely filled sp3 or p orbital makes the carbon electron-rich and it gives a negative
charge. Thus a carbanion will combine with any substance electron rich (e.g., electrophiles) which can
accept a pair of electrons.

The stability of carbanions is also influenced by resonance and inductive effects. For example, the
benzyl carbanion is much more stable than propyl carbanion. This is because the benzyl carbanion can
be stabilsed by resonance. Propyl carbanion (CH3CH2CH2-) has no resonance forms.

Benzyl carbanion

Stabilization of carbanions by inductive effects is in the opposite direction from that of carbonium
ions. Electron releasing groups (+I groups) make the carbanions less stable. Thus a primary carbanion
is more stable than a secondary, which in turn is more stable than a tertiary because of the +I effect
associated with alkyl groups.

Electron attracting groups (-I groups) will stabilize carbanion by partial removal of the
negative charge on the carbon.

3. CARBON FREE RADICALS: They are formed homolytic bond fission.

C : Z C˚ + Z˚

Carbon free radical

where Z and carbon have similar electronegativities.

The carbon atom in a carbon free radical uses sp 2 hybrid orbitals to

.
form three σ bonds. A half filled p orbital extends above and below
the plane of σ bonds. Thus carbon free radicals are electrically
neutral and have an unpaired electron. They are extremely reactive
because of the tendency of this unpaired electron to get paired at
the earliest opportunity. Free radicals combine with other free
radicals or with other molecules to produce large free radicals.

Carbon free radicals are named after the parent alkyl group and adding the word
free radical. For example:

Like carbocation, a tertiary free radical is more stable than a secondary, which in turn is more
stable than a primary. Free radicals are also stabilized by resonance.

4. CARBENE: A neutral species have divalent carbon with an unshared electron pair are termed
Carbenes. The carbene carbon has sextet of electrons and thus is electron deficient.
.. ..
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H–C–H Cl – C – Cl
Carbene Dichlorocarbene

TYPES OF ORGANIC REACTIONS

Organic reactions are classified as:
(1) Addition reactions (2) Substitution reactions (3) Elimination reactions (4) Rearrangement
reactions (4) Condensation reactions and (6) Isomerisation reactions.

1. Addition reaction
These are reactions in which atoms or group of atoms are added across unsaturated carbons
such that the double bonds become saturated and the triple bonds become double bonds or may
become saturated.
e.g. CH3–CH=CH2 + H2 Ni/∆ CH3–CH2–CH3
Propene Propane

2. Substitution reactions
These are reactions in which atoms or group of atoms attached to a carbon is replaced by
another atom or group of atoms.
e.g. CH4 + Cl2 sun light
CH3Cl + HCl

3. Elimination reactions
These are reactions which involve the removal of atoms or group of atoms from two adjacent
carbon atoms to form a multiple bond.
e.g. H H H H
R–C–C–H + KOH ∆ R–C = C – H + KX + H 2O
(alcoholic)
H X

4. Rearrangement reactions (Isomerisation reactions)

In these reactions atoms or group of atoms migrate from one site to another within the same
molecule. The product is always the structuralism isomer of the original compound.
e.g.
N-OH O
CH3-C-CH2-CH3 CH3-NH-C- CH2-CH3
Methyl ethylketoxime N-Methylpropianamide

5. Condensation reactions
In these reactions two reactant molecules of the same type or different directly join to form a
molecule with the loss of simple molecules like H2O, HCl, Br2 etc.
e.g. H H
CH3 - C = O + H2N-OH → CH3 - C=N-OH + H2O
Acetaldehyde Hydroxyl amine Acetaldoxime

HYBRIDIZATION

Tetravalency of carbon
Carbon has four valence electrons. It can complete its octet by sharing one electron each with four
monovalent atoms like hydrogen. Thus carbon can four covalent bonds which tratracovalency of carbon.

Hybridization
The process of mixing of atomic orbital of nearly equal energy to get hybridized orbitals of equal number
and same energy is known as hybridization.

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1. sp3 Hybridization: (Tetrahedral Hybridization)
In this one ‘s’ orbital and three ‘p’ orbitals undergo hybridization to give four sp 3 hybrid orbitals which
are oriented towards the corners of a regular tetrahedron.
e.g. CH4
A molecule of methane contains one carbon atom and four hydrogen atoms. The electronic
configuration is carbon is 1s 2 2s2 2p2. In the excited state one of the 2s electron jumps to the vacant
2pz orbital. 2s 2p
Ground state: ↑↓ ↑ ↑
2s 2p
Excited state: ↑ ↑ ↑ ↑

sp3 hybridization

Now the four half filed orbitals (2s,2px, 2py, 2pz) in the excited sate undergo hybridization to give four
sp3 hybrid orbitals all oriented towards the four corners of a tetrahedron at angle of 109 0 28’.

sp3
1090 28’
+ Px C
Pz sp 3 sp3
s
Py sp3

These four hybrid orbitals overlap with four 1s atomic orbitals of four hydrogen atoms to form four
carbon-hydrogen sigma bonds. The orbital picture of methane can be written as,
H H
σ s
sp3

sp3 C sp3 C 109028’

s H σ s
σ sp3 H
H H
σ s
H
H
Thus a molecule of methane has four carbon-hydrogen sigma bonds with a tetrahedral geometry with
the bond angle equal to 1090 28’.

2. sp2 Hybridization (Trigonal planar hybridization):

In this one‘s’ orbital and two ‘p’ orbitals undergo hybridization to give three sp 2 hybrid orbitals
which are oriented towards the corners of an equilateral triangle.
e.g. C2H4
A molecule of ethene contains two carbon atoms and four hydrogen atoms. The electronic
configuration is carbon is 1s 2 2s2 2p2. In the excited state one of the 2s electron jumps to the vacant
2pz orbital.
2s 2p
Ground state: ↑↓ ↑ ↑

2s 2p
Excited state: ↑ ↑ ↑ ↑

sp2 hybridization
In the excited state each of the two carbon atoms undergo sp 2 hybridization separately. The third
‘p’ orbital does undergo hybridization. Each of the three sp 2 hybrid orbitals point towards the corners
of an equilateral triangle with an angle of 1200.

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sp2
1200
+ Px C
sp2 sp2
s
Py
One sp2 hybrid orbital of each carbon overlaps with the other to form a carbon-carbon σ bond.
Two more sp2 hybrid orbitals of each carbon overlap with1s atomic orbitals of hydrogen atoms to form
carbon-hydrogen σ bonds. The unhybridized ‘p’ orbital on each carbon then overlaps sideways to form
a carbon-carbon π bond.
Pz Pz
s H σ π s H H H
sp 2
σ σ σ π σ
C sp2 sp2 C sp2 C C 1200
sp 2
σ σ σ
s H σ H s H σ H

Thus a molecule of ethene has one carbon-carbon σ bond, one carbon-carbon π bond, four
carbon-hydrogen σ bonds with a bond angle of 1200.

3. sp Hybridization (Linear or Diagonal hybridization)

In this one ‘s’ orbital and one ‘p’ orbital undergo hybridization to give two sp hybridized orbitals
which are linear.
e.g. C2H2
A molecule of ethyne contains two carbon atoms and two hydrogen atoms. The electronic
configuration is carbon is 1s 2 2s2 2p2. In the excited state one of the 2s electron jumps to the vacant
2pz orbital.
2s 2p
Ground state: ↑↓ ↑ ↑

2s 2p
Excited state: ↑ ↑ ↑ ↑

sp hybridization
In the excited state each of the two carbon atoms undergo sp hybridization separately, in
which the 2s and 2px hybridize to give two sp hybrid orbitals. The remaining two ‘p’ orbitals do not
undergo hybridization. The two sp orbitals lie linear with an angle of 180 0.

1800

+ C
s px sp sp

One sp hybridized orbital of each carbon overlaps with the other to form a carbon-carbon σ bond.
The other hybrid orbital of each carbon atom overlaps with the 1s atomic orbital of hydrogen to form
two carbon-carbon σ bonds. The unhybridised 2py atomic orbitals of both the carbon atom overlap
sideways to form one carbon-carbon π bond. Similarly, the 2pz orbitals of both the carbon atoms
overlap sideways to form another carbon-carbon π bond.
Py Py
π PZ
s σ sp π σ s π
H
C C H
H C σ C H
sp σ sp sp
σ π σ
PZ
PZ

Thus a molecule of ethyne has one carbon-carbon σ bond, two carbon-carbon π bonds and two
carbon-hydrogen σ bonds with a bond angle of 1800.

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BOND LENGTH
The inter-nuclear distance between two covalently bonded atoms in a molecule is known as bond
length. The unit of bond length is Angstrom (A0).

BOND ANGLE
In a covalent molecule, the angle made by two surrounding atoms with respect to the central atom is
termed as bond angle.

BOND ENERGY
Bond energy ids defined as the amount of energy required to break a bond. Its unit is Kcal/mol.

LOCALISEZED AND DELOCALIZED CHEMICAL BONDS

1. RESONANCE EFFECT (Mesomeric effect)
Resonance effect is the polarity produced in a molecule due to the delocalization of π electrons
caused by the overlap of p orbitals involved in the formation of π bonds (π- π overlap) or overlap of p
orbital of an atom (vacant or filled)with p orbitals involved in π bond formation (p- π overlap).

a. Delocalization of π electrons through (π- π overlap):

Delocalization of π electrons through π- π overlap occurs in conjugated system i.e. a molecule
where π bonds are separated by one σ bond only.
e.g. Buta-1,3-dene.

CH2=CH-CH=CH2 CH2-CH=CH-CH2-
+ -
CH2-CH=CH-CH2+

b. Delocalization of π electrons through (p- π overlap):

Delocalization of π electrons through p- π overlap occurs inin a system where p orbital of an
atom (vacant or filled) is separated from a π bond through one σ bond only.
e.g. Vinyl chloride
.... -
..
CH2 = CH - Cl:
.. CH2 –C = Cl:
..
+

Depending on the nature of the substituent group, two types of mesomeric effects are defined. They
are: i) -R effect ii) +R effect.

i) –R effect: An atom or group is said to have –R effect, if the direction of electron displacement
takes place towards it.
These groups contain an electronegative atom attached to key atom (atom attached
directly to carbon chain) by a multiple bond.

-R effect groups: -CHO, -NO2, -CN, -COOH, -SO3H

CH3 – CH = CH –CH =O CH 3 – CH – CH = CH – O..¯

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b) +R effect: An atom or group is said to have +M effect when the direction of electron displacement is
away from it.
Groups showing +M effect has alone pair of electron on the key atom.

+R effect groups: -Cl, -Br, -I, -OH, -NH2, -OCH3

2. HYPERCONJUGATION (NO BOND RESONANCE)

It is the delocalization of σ electrons through σ - π or σ - p overlap. The σ bond in conjugation
with the π bond or σ bond in conjugation with p orbital (vacant or filled)
e.g. Hyper conjugation in propene

In propene, the three C - H σ bonds of CH3 group are in conjugation with the π bond. The σ
electrons are transferred in the process to adjacent carbon-carbon bond; in turn the π electrons are
shifted to the terminal CH 2 group. Due to the participation of σ electrons in delocalisation, the bond
between carbon and hydrogen does not exist in the contributing structures and hence it is also referred
as No bond resonance.

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