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REACTIONS OF

ORGANIC
COMPOUNDS
Lecture 7
12.5 Reactions of Organic
Compounds
Learning Outcomes:
At the end of the lesson the students
should be able to :
 Explain covalent bond cleavage:
homolytic
heterolytic
Types of Covalent Bond
Cleavage/Fission

 All chemical reactions involved bond


breaking and bond making.

 Two types of covalent bond cleavage :-


 Homolytic cleavage
 Heterolytic cleavage
a) Homolytic Cleavage

 Occurs in a non-polar bond involving two


atoms of similar electronegativity.

 A single bond breaks symmetrically into


two equal parts, leaving each atom with
one unpaired electron.

 Formed free radicals.


Example:

X : X
X• + X•

free radicals

X• •X
b) Heterolytic cleavage

 Occurs in a polar bond involving unequal


sharing of electron pair between two
atoms of different electronegativities.

 A single bond breaks unsymmetrically.

 Both the bonding electrons are transferred


to the more electronegative atom.

 Formed cation and anion.


A: - + B+
anion cation
A is more
A:B
electronegative.

A + + B: -
cation anion
B is more
electronegative.
Reaction Intermediates

 a) Carbocation
 b) Carbanion
 c) Free Radical

They are unstable and highly reactive.


a) Carbocation

 Also called carbonium ion.


 A very reactive species with a
positive charge on a carbon atom.
 Carbocation is formed in heterolytic
cleavage.
Example :
δ + δ −
 (CH3)3C — Cl (CH3)3C+ + Cl-
carbocation anion

 Chlorine is more electronegative than


carbon and the C—Cl bond is polar.

 The C—Cl bond breaks heterolitically and


both the bonding electrons are transferred
to chlorine atom to form anion and
carbocation.
b) Carbanion

 isan anion counterpart


 a species with a negative charge on a
carbon atom.
 Carbanion is formed in heterolytic
cleavage.
example:
δ + δ −
 (CH3)3C — Li (CH3)3C- + Li+
carbanion
kation
b) Free Radical

A very reactive species with an unpaired electron.


Formed in homolytic cleavage.
Examples:
i)
free radicals
Cl –
Cl uv Cl●
+ Cl ●
ii)

C C ●C + ●C

iii)

H3C H H3C ● + ●H
Lecture 7
12.5 Reactions of Organic
Compounds
Learning Outcomes:
At the end of the lesson the students
should be able to:
 State the relative stabilities of primary,
secondary and tertiary free radicals,
carbocations and carbanions.
 Explain the inductive effect of alkyl group
towards the stability of carbocations and
carbanions.
 Define electrophile and nucleophile.
Relative Stabilities of Carbocations,
Carbanions and Free Radicals

 Carbocation, carbanion and free


radical can be classified into:
 Primary
 Secondary
 Tertiary
Carbocation Stability

 Thealkyl groups (electron-releasing


group) stabilise the positive charge
on the carbocation.

 Thestability of carbocation increases


with the number of alkyl groups
present.
Carbocation Stability:

H H R R
H C H < H C R <H C R < R C R
+ + + +
Methyl Primary Secondary Tertiary
cation 10 20 30

Increasing stability
Carbanion Stability

o Alkyl group and other electron-donating


groups destabilise carbanions.

o Electron withdrawing group (e.g:


halogen) stabilise carbanions through
the inductive withdrawal of electron
density
Carbanion Stability:

H H R R
H C H < H C R < H C R < R C R
- - - -
Methyl Primary Secondary Tertiary
anion 10 20 30

Increasing stability
Free-radical stability

 Thestability of free radical increases


as more alkyl groups are attached to
the carbon atom with unpaired
electron.
Free Radical Stability :
H R
H R
H C
. H < H C
. R < H C
. R <R C
. R
methyl Primary Secondary Tertiary
radical 10 20 30

Increasing stability
Reagents and sites of organic
reactions
A) Electrophile
 Means ‘electron loving’.
 An electron-deficient species and
accepting electron from an attacking
nucleophile.
 Can be either neutral or positively
charged
Examples of electrophiles :
 cations such as H+, H3O+, NO2+ etc.
 carbocations.
 Lewis acids such as AlCl3, FeCl3, BF3 etc.
 oxidizing agents such as Cl2, Br2 and etc.
electrophilic sites are molecules with
low electron density around a polar bond
Examples:
i) δ + δ - ii)
δ + δ -
-C = O (carbonyl) ; -C – X (haloalkanes)

iii)δ+ δ -
-C – OH (hydroxy compounds)
 b) Nucleophile
 means ‘nucleus loving’
 An electron-rich species and
electron-pair donor.
 A nucleophile can be either neutral
or negatively charged.
Examples of nucleophiles :

 anions such as OH-, RO-, Cl-, CN- etc.

 carbanions( species with a negative


charge on carbon atoms ).
Lecture 7
12.5 Reactions of Organic
Compounds
Learning Outcomes:
At the end of the lesson the students should
be able to explain the main types of organic
reactions:
 addition: electrophilic and nucleophilic
 substitution: electrophilic, nucleophilic and free
radical
 elimination
 rearrangement
4 Types of Organic
Reactions
 Addition
 Substitution
 Elimination
 Rearrangement
I) Addition Reaction

 A reaction in which atoms or groups add


to adjacent atoms of a multiple bond.
 Two types of addition :-

a) Electrophilic Addition
b) Nucleophilic Addition
a)Electrophilic Addition
 Initiated by an electrophile accepting
electron from an attacking nucleophile.
 Typical reaction of unsaturated compounds
such as alkenes and alkynes.
Example :

CH3CH=CH2 + Br2 CCl4 CH3CHBrCH2Br


Room
temperature
electrophile
b) Nucleophilic Addition

 Initiated
by a nucleophile, which
attacks an electrophilic site of a
molecule.
– Typical reaction of carbonyl compounds.
O CN
δ −
CH3 C CH3 + HCN CH3 C CH3
δ +
OH
II) Substitution Reaction
 A reaction in which an atom or group in
a molecule is replaced by another atom
or group.

 Three types of substitution :-


a) free radical substitution.
b) electrophilic substitution.
c) nuclephilic substitution.
a) Free-radical Substitution
 Substitution which involves free
radicals as intermediate species.
Example :

CH3CH3 + Cl2 uv light CH3CH2Cl + HCl


b) Electrophilic Substitution

 Typical reaction of aromatic compounds.


– The aromatic nucleus has high electron
density, thus it is nucleophilic and is prone
to electrophilic attack.
Example:

+ Br2 Fe Br + HBr
catalyst
electrophile
c) Nucleophilic Substitution
Typical reaction of saturated organic
compounds bearing polar bond as functional
group, such as haloalkane with alcohol.

Example :

δ +δ −
CH3CH2Br + OH-(aq) Δ CH3CH2OH + Br-(aq)
nucleophile
III) Elimination Reaction
– An atoms or groups are removed from
adjacent carbon atoms of a molecule to form
a multiple bond (double or triple bond).
– Results in the formation of unsaturated
molecules.
– Example :

 CH3CH2OH conc. H2SO4 CH2= CH2 + H2O



IV) Rearrangement
Reaction

 A reaction in which atoms or groups in a


molecule change position.
 Occurs when a single reactant reorganizes
the bonds and atoms.

Example : H
tautomerisme
H C C R H C C R
H OH H O
Exercises

1. Explain how the free radicals are


formed in homolytic cleavage.

2. Write an equation for the bromine-


bromine bond cleavage in the
bromination of methane. State the
type of bond cleavage.
3. Which would you expect to be the
most stable free radical ?

• CH2CH3 , (CH3)2 CH• , • CH3 , •


CH3