Reaction Mechanism in Organic Reactions

Introduction
In a chemical reaction, the reactant molecule undergoing
attack is called substrate and the attacking species is
called reagent. The substrate and reagent interact to give
the product.

The steps of an organic reaction showing the breaking and

making of new bonds of carbon atoms in the substrate
leading to the formation of final products through
transitory intermediates are called its reaction mechanism.
In short, the path or steps followed by a chemical reaction
during the formation of products is called its mechanism.
Bond fission
The breaking of chemical bond during chemical reaction
is called bond fission. A chemical bond breaks by the
following two ways.

1. Homolytic fission (bond cleavage) (Greek-homo-

same, lysis- loosening or breaking)
2. Heterolytic fission (bond cleavage) ( Greek-hetero-
different)
1. Homolytic fission: When chemical bond breaks such
that the bonded pair of electrons is distributed to each
fragment is called homolytic fission or hemolysis.
The odd electron species which are formed by
homolytic fission are called free radicals.

Examples:
2. Heteroytic fission: When chemical bond breaks such
that the bonded pair of electrons moves any one of
the fragments is called heterolytic fission or
heterolysis. Heterolytic fission gives charged species
ie. Carbanion (-) and Carbonium or Carbocation (+).

Examples:
Attacking species (reagents) involved in organic
reactions
Depending upon the types of substrate, there are three
types of attacking species ie. reagents.
1. Electrophile (Electrophilic reagent)
2. Nucleophile (Nucleophilic reagent)
3. Free radical
1. Electrophile: A reagent which is electron deficient
itself and can accept electron pair in a reaction is
called an electrophile. The name electrophile means
“electron loving” which attacks the region of higher
electron density (negative center) of the substrate. It
is denoted by E+. Examples:
 H+, F+(fluoronium ion), Cl+, Br+,I+, NO2+ (nitronium
ion), RN2+(diazonium ion), SO3H+ (sulphonium ion
or sulphonate ion), NH4+ (ammonium ion) (Positively
charged) and AlCl3, BF3, BCl3, FeCl3 ( Neutral
species (Lewis acids)).
2. Nucleophile: A reagent which is electron rich itself
and can donate electron pair in a reaction is called a
nucleophile. The name nucleophile means “nucleus
loving” which attacks the region of lower electron
density (positive center) of the substrate. It is denoted
by Nu:-. Examples: :

:
F-, Cl-, Br-, I-. OH-, NH R-O-R R-O-H R-NH2

:
3
:

Negatively charged and neutral species (Lewis bases)

Types of Organic Reactions

1. Substitution reaction ( Electrophilic substitution +

Nucleophilic substitution)
2. Addition reaction (Electrophilic addition +
Nucleophilic addition)
3. Elimination reaction
 4. Rearrangement reaction
Nucleophilic Substitution (SN) Reaction
When a substitution reaction involves in the initial
attack by nucleophile, the reaction is called nucleophilic
substitution reaction. This type of reaction is
characteristic of halo alkane (alkyl halide) in which
carbon atom develops positive pole due to more
electronegativity difference with halogen and it
undergoes nucleophile attack.

There are two mechanisms of nucleophilic substitution

reactions.
 A) Bimolecular nucleophilic substitution (SN2)
reaction.
B) Unimolecular nucleophilic substitution (SN1)
reaction.

Bimolecular nucleophilic substitution (SN2) reaction.

When the rate of a nucleophilic substitution reaction
depends on the concentration of both the substrate and
nucleophile (reagent), the reaction is second order and is
called bimolecular nucleophilic substitution (SN2)
reaction.

Example: Hydrolysis of primary (10) alkyl halide by

aqueous NaOH/KOH.
Mechanism:
The reaction is one step in which nucleophile (OH-)
obtained from aqueous NaOH attacks the substrate carbon
of primary alkyl halide to give a short lived transition
state (T.S.) which being unstable undergoes
decomposition to give alcohol.
Explanation:
a) Nucleophile attacks from the back side of carbon
because front side has halogen which brings high
electronic repulsion.
b) Nucleophile attacks on carbon atom of the substrate
easily because the substrate carbon is not crowded.
c) The energy required to break C-Cl bond is partly
provided by the energy liberated by the C-OH bond
formation.
Stereochemistry of SN2 reaction:
The hydroxyl ion (OH-) approaches the substrate carbon
from the side opposite to the chlorine atom (backside
attack). This is because both hydroxyl ion (OH-) and
chlorine atom is electron rich. The geometry of the
product is just inverted like an umbrella kept upside
down. This phenomenon of inversion in geometry of the
product is called Walden Inversion.
Unimolecular nucleophilic substitution (SN1) reaction.
When the rate of a nucleophilic substitution reaction
depends on the concentration of substrate only, the
reaction is first order and is called nucleophilic
substitution (SN1) reaction.

Example: Hydrolysis of tertiary (30) alkyl halide by

aqueous NaOH/KOH.
Mechanism:
Nucleophile (OH-) unlike in SN2 reaction cannot attack
carbon atom of substrate directly because C is more
crowded by methyl group (bulky group). The positive
charge of carbon atom is highly decreased because methyl
groups are electron releasing group (+ I effect).
So, the mechanism of SN1 reaction involves two steps.
Step I (Formation of carbonium ion ie. removal of
halide ion)
30 alkyl halide gets ionized to produce carbocation ie.
removal of halide ion (This is slowest step ie. RDS).

Step II (Nucleophilic attack)

Tertiary (30) carbonium ion can undergo attack by
nucleophile from front side as well as from the back. So,
there is formation of mixed products ie retention (same
geometry) or inversion (opposite geometry).
Give reason: Primary alkyl halide (CH3-X) undergoes
SN2 mechanism while tertiary alkyl halide (CH3)3-X)
undergoes SN1 mechanism.
In 10 alkyl halide, nucleophile can attack on the substrate
carbon atom directly because the substrate carbon atom is
not crowded because it is linked with H-atoms (small
group which is neither electron withdrawing nor electron
releasing group). So, substrate and reagent both involve in
rate determining step (SN2). On the other hand, the attack
of the nucleophile on crowded 30 alkyl halide is quite
difficult. Hence, halide ion is removed first (slowest step)
to form carbocation (SN1) and nucleophile attacks on
carbonium ion. Hence, 30alkyl halide undergoes by SN1
mechanism.
From another glance
The intermediate in an SN1 reaction is a carbocation. The
stability of that intermediate determines how favorable
that particular reaction is, so a more stable intermediate
means a more favorable reaction. Carbocations are quite
unstable on their own, but the inductive effect of nearby
C-C bonds provide some electron density to balance out
the positive charge, making the carbocation intermediate
more stable. Tertiary carbons have the largest number of
adjacent C-C bonds, the largest inductive effect, the most
stable carbocation intermediate, and are thus favored in
SN1.
Factors affecting SN1 and SN2 reaction
1. Nature of solvent: Polar solvent favors SN1 reaction
because in SN1 reaction mechanism, ionization takes
place.
2. Nature of nucleophile (Strength of nucleophilic
reagent): Strong nucleophile favors SN2 reaction
mechanism because in the reaction mechanism,
nucleophile directly attacks the substrate carbon.
3. Nature of substrate (Type of alkyl halide): Primary
alkyl halide favors SN2 reaction mechanism while
tertiary alkyl halide favors SN1 reaction mechanism.
It is due to steric and electronic factors. If strong
nucleophile and non-polar solvent is present, it favors
SN2 reaction whereas it favors SN1 reaction
mechanism in presence of weak nucleophile and
polar solvent.
4. Concentration of nucleophile: High concentration
of the nucleophile favors SN2 mechanism and low
concentration of the nucleophile favours the SN1
mechanism.
5. Structure of alkyl halide (Steric and electronic
factors): Generally, primary alkyl halides react by
SN2 mechanism, tert-alkyl halides by SN1 mechanism
and secondary alkyl halides by both SN2 and SN1
mechanisms. Thus in going from left to right in the
 following series of alkyl halides, the mechanism
changes from SN2 to SN1.

This is due to the fact that the electron density on α-

carbon atom goes on increasing by inductive effect of the
alkyl groups as we move from left to right. This increased
electron density on the α -carbon atoms repels the direct
attack of the nucleophile and thus retards SN2 reaction.
Moreover, the transition state of SN2 reactions becomes
more crowded as the size of the alkyl group increases.
This also slows down the SN2 reaction. On the other hand,
the increased electron density on the α -carbon atoms
increases the tendency of ionization of the alkyl halide
and thus favors SN1 mechanism. Furthermore, the
ionization relieves the steric hindrance and thus
accelerates SN1 mechanism.

6. Catalyst: There is no effect of catalyst on SN2

mechanism while SN1 path is catalyzed by Lewis
acids like AlCl3, BF3, BCl3 etc.

Points of difference between SN1 and SN2 reaction

Elimination reaction
Elimination reactions are those which involve the removal
of atom or group of atoms from two adjacent in the
substrate molecules to form a multiple bond. Elimination
Reaction may be regarded as reverse of addition
reactions. In this reaction two sigma (σ) bonds are lost
and a new pie (π) bond is formed. Saturated compounds
become unsaturated.
In other words, it is the opposite of addition reaction. In
such reaction, there is removal of electropositive and
electronegative radicals of a molecule from adjacent
carbon atoms of substrate molecule. One π bond is formed
as a result of the breakage of two σ bonds.
Examples:

Types of elimination reactions

1. Bimolecular elimination (E2) reaction
2. Unimolecular elimination (E1) reaction

1. Bimolecular elimination (E2) reaction

When the rate of an elimination reaction depends on
the concentration of substrate and nucleophile (base),
the reaction is second order and is called bimolecular
elimination (E2) reaction.
i) Order and molecularity of reaction =2.
ii) Both substrate and reagent involve in RDS.
iii) The concentrations of both affect the rate.
iv) Primary alkyl halide with alc. NaOH/KOH
favors E2 mechanism
 Mechanism
E2 like SN2, is also a one step process in which the
abstraction of the proton from the β-carbon and the
expulsion of the leaving group i.e. halide ion etc from the
α –carbon atom occur simultaneously. The mechanism for
such a reaction may be represented as follows.

OR

Potassium ethoxide is a very strong nucleophile. It

withdraws proton (H+) from β-carbon and halogen is also
eliminated. In other words, in these reactions, the two
groups are eliminated i.e. H atom and Br are trans to each
other and hence E2 reactions are generally trans
elimination reactions.
2. Unimolecular elimination (E1) reaction
When the rate of an elimination reaction depends on
the concentration of substrate only, the reaction is
first order and is called unimolecular elimination (E1)
reaction.
i) Order of reaction =1, molecularity of reaction
=2.
ii) Only substrate involves in rate determining step
(RDS)
iii) The concentrations of substrate affect the rate.
iv) Tertiary alkyl halide with alc. NaOH/KOH
favors E1 mechanism

Mechanism
E1 like SN1 reactions are also two-step processes. The first
step involves the slow ionization of the alkyl halide to
give the carbonium ion (slowest step ie. RDS) and the
second step involves the fast abstraction of a proton by
the base from the adjacent β-carbon atom leading to the
formation of an alkene. Thus,

OR
Saytzeff rule:
If the dehydrohalogenation of an alkyl halide can yield
more than one alkene, the major product is the most
highly substituted alkene. This is elimination reaction and
the rule is called Saytzeff’s rule.

In accordance with the Saytzeff Rule, the main product is

the di-substituted alkene, 2-butene (80%), rather than the
mono-substituted, 1-butene (20%).
Factors affecting E1 and E2 reaction (Same as SN1 and
SN2)
1. Nature of solvent: Polar solvent favors E1 reaction
because in E1 reaction mechanism, ionization takes
place.
2. Nature of nucleophile (Strength of nucleophilic
reagent): Strong nucleophile favors E2 reaction
mechanism because in the reaction mechanism,
nucleophile directly attacks the substrate carbon.
3. Nature of substrate (Type of alkyl halide): Primary
alkyl halide favors E2 reaction mechanism while
tertiary alkyl halide favors E1 reaction mechanism. It
is due to steric and electronic factors. If strong
nucleophile and non-polar solvent is present, it favors
E2 reaction whereas it favors E1 reaction mechanism
in presence of weak nucleophile and polar solvent.
4. Concentration of nucleophile: High concentration
of the nucleophile favors E2 mechanism and low
concentration of the nucleophile favors the E1
mechanism.
5. Structure of alkyl halide (Steric and electronic
factors): Generally, primary alkyl halides react by
E2 mechanism, tert-alkyl halides by E1 mechanism
and secondary alkyl halides by both E2 and E1
mechanisms. Thus in going from left to right in the
 following series of alkyl halides, the mechanism
changes from E2 to E1.

This is due to the fact that the electron density on α-

carbon atom goes on increasing by inductive effect of the
alkyl groups as we move from left to right. This increased
electron density on the α-carbon atoms repels the direct
attack of the nucleophile and thus retards E2 reaction.
Moreover, the transition state of E2 reactions becomes
more crowded as the size of the alkyl group increases.
This also slows down the E2 reaction. On the other hand,
the increased electron density on the α-carbon atoms
increases the tendency of ionization of the alkyl halide
and thus favors E1 mechanism. Furthermore, the
ionization relieves the steric hindrance and thus
accelerates E1 mechanism.

6. Catalyst: There is no effect of catalyst on E2

mechanism while E1 path is catalyzed by Lewis acids
like AlCl3, BF3, BCl3 etc.

Points of difference between E1 and E2 reactions

Selected Questions
1. Describe the bimolecular nucleophilic substitution
reaction in haloalkane with suitable example. What
type of solvent is favor for this reaction? Write down
 the differences between SN1 and SN2 reaction.
[2+1+2].
2. Write the reaction mechanism of
dehydrohalogenation of tertiary butyl bromide by
alcoholic caustic soda. Mention the factors governing
the mechanism of E1 reaction. [3+2].

3. What is meant by SN reaction? Explain the

mechanism for the nucleophilic reaction with the
inversion of configuration. Why inversion product
predominates more than the retention in SN1
reaction? [1+3+1].
4. What do you mean by elimination reaction? Write the
mechanism for dehydrohalogenation in primary alkyl
halide. Show your acquaintance to Saytzeff rule.
[1+2+2].
5. What are the differences between E1 and E2
reactions? Explain the reaction mechanism for the
reaction of primary alkyl halide with alcoholic
NaOH. [2+3].
6. Why SN1 reaction does give both retention and
inversion isomers but SN2 gives only inversion
isomer? Write the mechanism for the reaction
between bromoethane and aq. NaOH. [2+3].
7. Write the reaction mechanism of tertiary alkyl halide
with a) Aqueous NaOH b) Alcoholic NaOH
[2.5+2.5].
 8. a) How does the reaction of bromoethane occur with
aqueous caustic soda (NaOH)?
b) Explain the reaction mechanism of
0
dehydrohalogenation of 1 alkyl halide. [2.5+2.5].

Why inversion product predominates more than the

retention in SN1 reaction?

It may have to do with the structure and reactivity of the

carbocation. Although theoretically planar, the
carbocation might be more sterically hindred from the
front side; also very reactive carbocations may react so
fast that the leaving group is not completely removed
from the area, and rear approach by the nucleophile
preferably happens. There are several factors to consider
like the size and reactivity of the carbocation, the size and
reactivity of the nucleophile, the solvent, the temperature,
and concentrations.

References
1. A text book of Organic Chemistry: Arun Bahl and BS
Bahl, S Chand Publication
2. Organic Chemistry: Morrison and Boyd, Allyn and
Bacon, Inc. University Book Stall
3. A text book of Engineering Chemistry: Ram Kumar
Sharma and et. al (2011), Atharai Publication
4. Google search for some images.