CHAPTER 2

ORGANIC REACTION TYPES

CO1
= Have the ability to explain the concept
of hybridization in describing bonding
between atoms in organic molecules.

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Why and how chemical reactions take place
What kind of reaction occur
How reaction occur
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Types of organic reaction
Addition reaction
Elimination reaction
Substitution reaction
Rearrangement reaction

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Addition reaction
Two reactants add together to form single
product with no atoms left over
Characteristic of compounds containing
double and triple bond
Less energy to break p than s bond (app.
15kJ/mole weaker)
Electrophilic addition reaction (Br
2
+ =)
Nucleophilic addition reaction (C=O + HCN)

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Elimination reaction
Opposite of addition reactions.
Occur when single reactant splits into two
products, often with formation of a small molecule
such as water or HBr.
Ex. Acid-catalyzed reaction of an alcohol to yield
water and an alkene
E1, E2, E1cB

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Substitution reaction
Two reactants exchange parts to give two new
products
Replacement or substitution of one or more
atoms or groups of compound by other atoms
or groups
Free radical substitution
Ionic Substitution
Electrophilic substitution (benzene + NO
2
+
)
Nucleophilic substitution (S
N
1 and S
N
2)
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Rearrangement reaction
Occur when a single reactant undergoes a
reorganization of bonds and atoms to yield
isomeric product
Atoms/groups shift from one position to
another within the substrate molecule itself
giving a product with a new structure
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Mechanism
Reaction mechanism: overall description of
how a reaction occurs
Describes in detail exactly what takes place at
each stage of chemical transformation-which
bonds are broken/formed and in what order.
Also account for all reactants used and all
products formed
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Two ways in which a covalent two-electron
bond can break/form
Symmetrically/homolytic ( ) radical reaction
Unsymmetrically/heterolytic ( ) polar reaction
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Radical reaction
Not as common as polar reactions
Radicals react to complete electron octet of valence shell
A radical can break a bond in another molecule and
abstract a partner with an electron, giving substitution in
the original molecule
A radical can add to an alkene to give a new radical,
causing an addition reaction

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Radical reaction
Initiated by free radicals
Example: methane chlorination
Initiation: irradiation with UV light begins the
reaction by breaking the relatively weak Cl-Cl
bond to form chlorine radical
Propagation: Chlorine radical collides with
methane, abstract hydrogen to give HCl and
methyl radical (*CH
3
). Which reacts with Cl
2

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Radical reaction




Termination: two radicals collide and combine
to form stable product
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Polar reactions
Molecules can contain local unsymmetrical
electron distributions due to differences in
electronegativities
This causes a partial negative charge on an atom
and a compensating partial positive charge on an
adjacent atom
The more electronegative atom has the greater
electron density
Elements such as O, F, N, Cl more electronegative
than carbon

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Polar reactions
An electrophile, an electron-poor species, (neutral or
+ve) combines with a nucleophile, an electron-rich
species (neutral or ve)
The combination is indicate with a curved arrow
from nucleophile to electrophile
Example: addition of HBr to Ethylene
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Polar reactions
Using curved arrows
Rule 1: electrons move from a nucleophilic
source(-ve or neutral) to an electrophilic sink (+ve
or neutral)
Rule 2: octet rule must be followed

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Describing a Reaction: Intermediates
If a reaction occurs in more
than one step, it must involve
species that are neither the
reactant nor the final product
These are called reaction
intermediates or simply
intermediates
Each step has its own free
energy of activation
The complete diagram for the
reaction shows the free energy
changes associated with an
intermediate
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