CHAPTER 6

ORGANIC REACTION MECHANISM

Substrate: A substrate may be defined as the reactant that contains
carbon atoms. Some of whose bonds with other atoms are broken and
some new ones is formed as a result of reaction with attacking reagent.
Mechanism: The steps of an organic reaction depicting the breaking
and making of new bonds of carbon atoms in the substrate leading to
the formation of new product through intermediates, are often
referred to as its mechanism
Substrate intermediate product
Carbonium ion: An ion containing a positively charged carbon center is
called carbonium ion. Let us consider the heterolytic fission of C-X
present in an organic molecule. If the atom X has greater
electronegativity than the carbon atom, the former takes away the
bonding electron pair and becomes negatively changed while an ion
bearing positive charge is produced.

pg. 1
Carbanion ions: An organic ion with a pair of available electrons and
negative charge on the central carbon atom is called carbanion ions.
Let us consider, the heterolytic fission of the bond C-X present in an
organic molecule. If the carbon has greater electronegativity than the
atom X, the former takes away the bonding electron pair and acquires a
negative charge while positive ion X+ is produced.

Attracting reagent: It is of two types:

1. Electrophile: Electron loving species is known electrophile.
Attacking reagent that consists of positive charge is called
electrophile eg. carbonium ions, nitrosonium ions (N+O), diazonium
ions (C6H5 N2+)

2. Nucleophile: Nucleus loving group is called nucleophile.

Nucleophile bears negative charge due to excess electron pair e.g.:
carbanion ion, chloride ions, Cyanide ion etc.

SUBSTITUTION REACTION

pg. 2
 Reactions proceeding by the replacement or substitution of one
or more atoms or groups of a compound by other atoms or group
are referred as substitution reaction.

a. Nucleophilic substitution reaction:

When the substitution reaction is brought about by a
nucleophile, the reaction is termed as nucleophilic substitution
reaction (SN). Hydrolysis of alkyl halide by aqueous alkalis is the
best example of SN reaction

These reactions may be divided into classes.

1. SN2 (Bimolecular nucleophilic substitution reaction)
2. SN1 (unimolecular nucleophilic substitution reaction)

SN2 Reaction: When the rate of a nucleophilic substitution

reaction is dependent both on concentration of the subtract and
the nucleophile the reaction is of 2nd order and is represented as
S N2
Rate ∝[Substrate] [nucleophile]

The rate determining step involves the participation of both the

substrate and nucleophile molecule. Thus, the transition state of
such a reaction may be represented as

pg. 3
 When hydroxide ion collides with methyl bromide molecule at the
first face with sufficient energy, a C-OH bond is formed, and C-Br
is cleaved with the repulsion of bromide ion. Thus, the transition
state may be pictured as the structure in which both OH and Br
are partially bonded to the carbon atom of methyl group.
Furthermore C-Br bond is not completely broken, and C-OH is not
completely formed. Hydroxide ion has diminished negative charge
because it has started to share its electrons with carbon atom
while bromine ion carries negative charge because it has started
removing its shared pair of electrons from carbon atom and finally
the product is formed. The energy needed for the cleavage of C-Br
bond is partly provided by energy liberate by the C-OH bond
formation. IT can be illustrated by energy profile diagram.

pg. 4
 Stereochemistry of SN2 reaction
The SN2 reactions proceed through complete inversion of
configuration. When alkyl halide reacts with aqueous NaOH, the
configuration of central carbon of alkyl halide changed into the
alcohol. If the alkyl halide is levorotatory, then the product
alcohol will be dextrorotatory and vice versa. This type of
inversion is called Walden inversion.

pg. 5
 Reactivity
The rate of the SN2 reaction in varieties of substrate revealed that
the relative reactivities of the alkyl halide with nucleophile follow
the following order.

CH3X ¿ 1o alkyl halide > 2o alkyl halide > 3o alkyl halide

The order of reactivity can be explained on the basis of steric

effect and inductive effect.
As the size of substitution at halogen bonded carbon increase the
rate of SN2 reaction falls because the large substituent causes
greater steric effect. Because of the steric hinderance there is
difficult to attack the central electron deficient carbon by
incoming nucleophile. In alkyl halides, the size of substituents
increases from 1° to 3° thus, steric effect also increases which
slowed down the reactivity of SN2 reaction.

pg. 6
 Inductive effect also plays vital role to decrease reactivity of
alkyl from 3° to 1° towards SN2 reaction.

SN1 reaction (unimolecular nucleophilic substitution

reaction)
when the rate of a nucleophilic substitution reaction is
dependent only upon the concentration of the alkyl halide and is
independent of the concentration of the nucleophile, the reaction
is of 1st order and is called SN1 reaction.

Rate ∝ [ Substrate]

Mechanism of SN1 reaction consists of two steps.

1. The first step is the ionization of alkyl halide to form
carbocation. This step hence rate determining step.

pg. 7
 2. The second step is the attack of nucleophile to the carbocation
to form the product.

In SN1 reaction the first step i.e. carbocation formation step and
hence is rate determining step. The first step involves only the
substrate molecule so that rate depends only upon the
concentration of substrate.

Stereochemistry of SN1 reaction

pg. 8
 The stereochemistry of the product of SN1reaction has partial
racemization with slight excess of inversion of configuration.

Reactivity: The reactivity of alkyl towards SN1 reaction

increase on going from primary to tertiary alkyl halides.

CH3X¿ 1oalkyl halide < 2o alkyl halide < 3o alkyl halide

The reactivity of alkyl halide towards SN1 reaction can be

explained on the basis of formation and stability of
carbocation. The more stable the carbocation, faster and the
rate of SN1 reaction is greater with tertiary alkyl halide than
that with 2° and then 1° alkyl halide.
Energy profile diagram of SN1 reaction

pg. 9
 Factors affecting SN reaction

1.Nature of the alkyl halides: Generally primary alkyl halides react by

SN2 mechanism, tert. Alkyl halides SN1mechanism and secondary alkyl
halides by both SN1 and SN2 mechanism. This is due to the fact that the
electron density on -carbon atom goes on increasing by inductive effect
of the alkyl group as we move from primary to tertiary. This increase
electron density on the α -Carbon repels the direct attack of the
nucleophilic and thus retards SN2reaction. Moreover the transition
state of SN2reaction becomes more crowed as the size of alkyl group
increases. This slows down the SN2 reaction. On the other hand, the
increase electron density on the α -Carbon atoms increase the tendency
of ionization of alkyl halides and thus, favors SN1 reaction.
2.Nature of nucleophile: powerful nucleophiles like alkoxides,
hydroxides favors SN2 mechanism while weak nucleophile like water,
alcohol favors SN1 reaction mechanism. Furthermore, high
concentration of nucleophile favors SN2 reaction mechanism and low
concentration favors SN1mechanism.
3.Nature of solvent: The higher the polarity of the solvent the greater is
the tendency of the alkyl halide to undergo substitution by SN1 reaction.
4.Nature of the halogen atom: The nature of the halogen atoms does
not have much influence on reaction mechanism through it does alter
the rate of reaction which follows the order.

R- I > R-Br > R-Cl (for both SN1 and SN2 reaction)

pg. 10
SN1 REACTION SN2 REACTION
It is unimolecular substitution It is bimolecular substitution
reaction and follows 1st order reaction and followed second
kinetics order kinetics.
It involves two step mechanism. It involves the single step
mechanism.
It proceeds by the formation of It proceeds by the formation of
carbocation. transition state which involves
the partial bonding of nucleophile
and Leaving Group.
Rate of reaction depends on the The rate of reaction depends on
concentration of substrate only. the concentration of both
substrate and nucleophile.
Stereochemistry of the product is Stereochemistry of the product is
found with partial racemization found with complete inversion of
plus inversion. that is both the configuration which is also called
retention and inversion of Walden inversion
configuration are formed but the
later is in slightly excess.
Tertiary alkyl halides undergo SN1 Primary alkyl halides undergo SN2
reaction and the reactivity reaction and the reactivity
o o
sequence is 3> 2 > 1 >CH3X sequences is CH3X> 1o >2o >3o
A weak nucleophile favours the A strong nucleophile favours the
SN1 reaction. SN2 reaction
Rearrangement of methyl groups No rearrangement of methyl
may take place to form more group is possible during that
stable carbo cation reaction.
Reaction is favoured by polar but the reaction is favoured by
solvent. nonpolar solvent.
Differences between SN1 and SN2 reaction

pg. 11
 Electrophilic substitution reaction
When a substitution reaction involves an attack by electrophile,
the reaction is referred to as electrophilic substitution reaction.
The substitution reaction of benzene is the best example of
electrophilic substitution.

The benzene ring with its π electron behaves as an electron rich

system. The electrons in the π clouds are readily available to
form new bonds with electron deficient species, the
electrophile.

Step1: Generation of electrophile either by spontaneous

dissociations of the reagent or by acid catalyzed dissociation
E-Nu E+ + Nu
E-Nu + A E+ + Nu-A-

Step2: Formation of π complex due to loose association of

electrophile with aromatic ring.

pg. 12
 Step3: A proton is then eliminated from the complex by a base
yield final substitution product.

Electrophilic substitution reaction of arene

1. Halogenation
2. Nitration
3. Sulphonation
4. Friedel crafts reaction

pg. 13
 5.

pg. 14
pg. 15
 differences between E1 and E2 reaction
E1 Reaction E2 Reaction
It is unimolecular elimination It is bimolecular elimination
reaction reaction
It follows first order kinetics.
It follows second order
i.e, the rate of reaction kinetics. i.e, the rate of
depends upon concentration reaction depends upon
of substrate only. concentration of substrate as
well as reagent.
It involves two step It involves single step
mechanism. mechanism.
Reaction mechanism involves Reaction mechanism involves
formation of carbocation. formation of transition state.
Rearrangement may occur as No side reaction occurs.
side reaction.
Polar solvent favours E1 Non-polar solvent favours E2
reaction. reaction.
Better leaving groups favour Leaving groups do not have
the E1 reaction. Since they significant influence in E2
make ionization easier and reaction.
faster.

pg. 16
ELIMINATION REACTION
When two or more atoms or groups attached to the adjacent carbon
atoms in the substrate molecule are eliminated to form a multiple
bond, then such type of reaction is called elimination reaction.
Dehydrohalogenation of alkyl halide with alcohol KOH is the best
example of elimination reaction

It is also of two types.

Biomolecular elimination reaction (E2 reaction)
Unimolecular elimination reaction (E1 reaction)

E2 reaction: When the rate of an elimination reaction is dependent both

on concentration of reactant (substrate) and the nucleophile, the
reaction is of 2nd order and is called E2 reaction. E2 reaction is one step
process in which the abstraction of the proton from β−¿Carbon and
expulsion of the leaving group i.e. halide ion etc from α −¿Carbon atom
occurs simultaneously

pg. 17
ENERGY PROFILE DIAGRAM

ORIENTATION: The elimination reaction of unsymmetrical alkyl halides

usually yields a mixture if alkenes.

pg. 18
The orientation of E2 reaction is governed by an empirical rule called
Say Zeff’s rule. It states that in elimination reaction of unsymmetrical
alkyl halides the alkene having greater no. of alkyl groups attached to
doubly bonded carbon atoms is the preferred product.

REACTIVITY: Going from primary to tertiary alkyl halides the structure

becomes more branched at carbon carrying halogen atom. The high
branching, on the other hand provides a greater number of β -hydrogen
to be attached by base and on the other hand elimination is favored to
from highly branched alkene. Hence order of reactivity of alkyl halides
toward E2 reaction is
3° alkyl halide > 2° alkyl halide > 1° alkyl halide

(Uni molecular elimination reaction) E 1 reaction: When the rate of

elimination reaction is dependent only upon concentration of the
substrate and is independent if the concentration of the nucleophile
the reaction is of 1st order and is called E1 reaction.
Rate ∞ [substrate]
Rate = k [substrate]
E1 reaction involves two steps:
Step1: Heterolytic fission of alkyl halides to form carbocation

pg. 19
It is a slow step and hence rate determining step.

Step2: Base abstracts a proton from β -Carbon to produce alkene

Since the tertiary carbocation is highly stable, generally tertiary alkyl

halide follows E1 mechanism. For example, the reaction mechanism of
tertiary butyl chloride on heating with alcoholic KOH may be explained
as above.
ENERGY PROFILE DIAGRAM

pg. 20
Orientation: The orientation of the products in E1 reaction follows the
Saytzeff’s rule. It states that when there is possibility of formation of
more than one alkene, then more highly branched alkene is to
preferred product or in another way when there is possibility of
formation of more than one alkene, alkene with maximum number of
alkyl group is the major product.

pg. 21
Reactivity: Reactivity of E1 reaction depends upon formation of
carbocation. Formation of carbocation determine the order of reactivity
of alkyl halides. The stability of carbocation increases on going from 1°
to 3°. This is because of the increasing +I effect of alkyl groups bonded
to the positively charge and increase the stability.
More stable the carbocation faster it is formed. That means tertiary
carbocation is formed in the rapid rate than the secondary pr primary
carbocation. Therefore, the reactivity order of alkyl halides towards E 1
reaction is
3° alkyl halide > 2° alkyl halide > 1° alkyl halide

FACTORS AFFECTING E1 AND E2 REACTION

1. Nature of substrate
2. Nature of nucleophile
3. Nature of solvent
4. Nature of leaving group

Nature of substrate: E2 reaction mechanism involves a single step, the

stability of alkene determines reactivity of alkyl halides. The more

pg. 22
stable the alkenes faster it is formed. And highly branched alkenes are
more stable, so alkyl halide follow the following reactivity order
towards E2 reaction,
3° > 2° > 1° > CH3X

In E1 reaction mechanism formation of carbocation is a rate

determining step. Therefore, stability of carbocations formed
determines the reactivity of alkyl halides tertiary carbocation are more
stable than primary carbocations so the order of reactivity of alkyl
halides towards E1 reaction is
3° > 2° > 1° > CH3X

Concentration of base (nucleophile): Rate of E1 reaction does not

depend upon concentration of the base. But the nature and
concentration of the base has significant effect on E 2 reaction. It is
found that the stronger base at high concentration increases the rate of
E2 reaction.
Nature of solvent: Polar solvent favors the E1 mechanism and non-
polar solvent favors E2 mechanism.
Nature of leaving group: Both of the mechanism needs good leaving
group. Better leaving groups favors the E1 mechanism. Since they make
ionization easier and faster

pg. 23
pg. 24