0% found this document useful (0 votes)
4 views35 pages

Chapter 6

The document outlines various types of organic reactions, specifically focusing on substitution and elimination reactions. It details the mechanisms of SN1 and SN2 reactions, including their kinetics, stereochemistry, and factors affecting their rates. Additionally, it discusses elimination reactions, particularly the E2 mechanism and Saytzeff's rule regarding product formation in dehydrohalogenation processes.

Uploaded by

Kamla Bhandari
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
4 views35 pages

Chapter 6

The document outlines various types of organic reactions, specifically focusing on substitution and elimination reactions. It details the mechanisms of SN1 and SN2 reactions, including their kinetics, stereochemistry, and factors affecting their rates. Additionally, it discusses elimination reactions, particularly the E2 mechanism and Saytzeff's rule regarding product formation in dehydrohalogenation processes.

Uploaded by

Kamla Bhandari
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

TYPE OF ORGANIC REACTIONS

Chemical reactions involving organic compounds are called Organic


reactions. The basic organic chemistry reaction types are: -
➢ Substitution reactions,
➢ Elimination reactions,
➢ Addition reactions,
➢ Rearrangement reactions,
➢ Pericyclic reactions,
➢ Photochemical reactions and
➢ Redox reactions.

[Link]@[Link]
1. SUBSTITUTION REACTIONS
A reaction in which the functional group of one chemical compound
is substituted by another group or it is a reaction which involves the
replacement of one atom or a molecule of a compound with
another atom or molecule, is called substitution reaction.
Those substitution reactions which are due to nucleophiles are Nucleophilic substitution (SN)
reactions (investigated by Ingold and his co-workers).

There are two types of SN reactions depending upon the nature of the substrate,
the nucleophile, the leaving group and the solvent as follows: -
[Link]@[Link]
THE SN2 REACTION
SN2 stands for bimolecular nucleophilic substitution reaction. Thus,
nucleophilic substitution reactions which follow second order kinetics is
called bimolecular nucleophilic substitution (SN2) reaction.

The rate of a second-order reaction depends upon the concentrations of both the
reactants or the concentration of alkyl halides and the nucleophile present in the
reaction.
Thus, Rate α [Substrate] [Nucleophile]
[Link]@[Link]
Example: The process of hydrolysis of methyl bromide to methyl alcohol using aq. NaOH in
which hydroxyl ion displaces the bromide ion.

CH3Br + OH-→ CH3OH + Br-


OR,

Here, the nucleophile attacks the back side from leaving group. In T.S., both OH
and Br lies as far apart bond are partial. Other C - H bonds lie in one plane but C-
OH bond and C-Br bond lie in perpendicular to such plane.
In this case, Rate = k [CH3Br] [OH-]

[Link]@[Link]
STEREOCHEMISTRY OF SN2 REACTION
Since purely SN2 reactions show 100% inversion in stereochemical configuration, it is clear that
these Reactions occur through a backside attack.

Thus, this reaction proceeds with complete stereo-chemical inversion (an example
of stereo-specific reaction). This inversion in configuration is also called ‘Walden
Inversion’.
Example:

[Link]@[Link]
THE SN2 REACTION – REACTIVITY
In the SN2reaction, the big barrier is steric hindrance. Since the SN2
proceeds through a backside attack, the reaction will only proceed if the
empty orbital is accessible. The more groups that are present around
the vicinity of the leaving group, the slower the reaction will be. That’s
why the rate of reaction proceeds from
primary (fastest) > secondary >> tertiary (slowest).
Methyl halide > 10 halide > 20 halide >> 30 halide
Relative rates: 30 1 0.02 0.00001 ≈ 0
Thus, the important factor behind this order of reactivity is a steric
effect.
[Link]@[Link]
ENERGY PROFILE DIAGRAM FOR
A SN2 REACTION

Figure: Energy profile diagram showing SN2 mechanism


Here, transition state occupies at the peak of curve as in the above figure where no
bond is formed or attacking and leaving species form complex compound as
activated complex.

[Link]@[Link]
FACTORS AFFECTING SN2 REACTION MECHANISM
1. Nature of Substrate (the alkyl group) -
To maximize the rate of the SN2 reaction, the back of the substrate must be as unhindered as possible. Overall, this
means that methyl and primary substrates react the fastest, followed by secondary substrates. Tertiary substrates do
not participate in SN2 reactions, because of steric hindrance.
2. Nature of nucleophile -
Strong nucleophile or strong base or anionic nucleophile (preferably negatively charged nucleophile) always favor
SN2 mechanism.
For example: 𝑂𝐻− is a better nucleophile than water, and 𝐼 − is a better nucleophile than 𝐵𝑟 − (in polar protic
solvents).
3. Nature of the leaving group (the halogen atom) -
Good leaving groups like weak base favor SN2 mechanism. Examples of good leaving groups are therefore the halides
(except fluoride, due to its strong bond to the carbon atom) and tosylate, whereas 𝑂𝐻 − and H2𝑁 − are not.
4. Nature of the solvent -
Polar aprotic solvents (like tetrahydrofuran) are better solvents for this reaction than polar protic solvents because
polar protic solvents will hydrogen bond to the nucleophile, hindering it from attacking the carbon with the leaving
group. A polar aprotic solvent with low dielectric constant or a hindered dipole end will favor SN2 manner of
nucleophilic substitution reaction.
Examples: dimethyl sulfoxide, dimethyl formamide, acetone, acetonitrile etc.
In short, Polar aprotic (e.g. DMSO, acetone) prefer SN2 mechanism.
[Link]@[Link]
THE SN1 REACTION
SN1stands for unimolecular nucleophilic substitution reaction. Thus,
nucleophilic substitution reactions which follow first order kinetics is called
Unimolecular nucleophilic substitution (SN1) reaction.

The rate of reaction depends upon the concentration of substrate and not upon nucleophile.
Thus, Rate ∝ [Substrate]

[Link]@[Link]
This means it involves following two steps:
Step I: The carbon-halogen bond is a polar covalent bond. The cleavage of this bond allows the
removal of the leaving group (halide ion). When the halide ion leaves the tertiary butyl bromide, a
carbocation intermediate is formed. As mentioned earlier, it is the rate determining step.

+ −
C X C +X

It is important to note that the breaking of the carbon-halogen bond is endothermic.


Step II: In the second step of the SN1 reaction mechanism, the carbocation is attacked by the
nucleophile to give products.

C + Nu C Nu

[Link]@[Link]
Example: the process of hydrolysis of tertiary butyl bromide with aq. NaOH involves following
two steps:
Step I: Formation of Carbocation (Rearrangement to give stable planar carbonium ion if
necessary)

Step II: Attack of carbonium ion from front and back side attack but back side attack
predominates.

[Link]@[Link]
STEREOCHEMISTRY OF SN1REACTION
The carbocation intermediate formed in step-1 of the SN1 reaction mechanism is an
sp2 hybridized carbon. Its molecular geometry is trigonal planar, therefore allowing
for two different points of nucleophilic attack: left and right as follows: -

The reaction proceeds with the complete racemization but inversion product
predominate.
[Link]@[Link]
THE SN1REACTION – REACTIVITY
In the SN1 reaction, the big barrier is carbocation stability. Since the first
step of the SN1 reaction is loss of a leaving group to give a carbocation,
the rate of the reaction will be proportional to the stability of the
carbocation. Carbocation stability increases with increasing substitution
of the carbon (tertiary > secondary >> primary) as well as with
resonance.
The decreasing order of reactivity of alkyl halides to SN1 - reaction is:
30 RX > 20 RX >10 RX > CH3X
Thus, the important factor for this is due to the stability of Carbocation as
a result of hyper - conjugation effect.

[Link]@[Link]
ENERGY PROFILE DIAGRAM
FOR SN1REACTION –

Figure: Energy profile diagram showing SN1 mechanism

[Link]@[Link]
FACTORS AFFECTING SN1 REACTION MECHANISM
Nature of Substrate (the alkyl group)
Tertiary alky halides favor SN1 mechanism. Also, substrates which yield most stable carbocations
like tertiary, allylic and benzylic halides favor SN1 mechanism or 3o > 20 ≫ 10.

Nature of nucleophile :Neutral or weak nucleophile prefer SN1 mechanism.


Nature of the leaving group (The halogen atom)
The C-X bond breaks in the rate determining step of SN1, just as it does in SN2. Again, these are
determined by the C-X bond strength and the stability of X after it has left. Hence, Good leaving
groups like weak base favor SN2 mechanism and good leaving groups with stable anions favor SN1
mechanism. The ease of elimination of the leaving group is I- > Br- > Cl- > F-, therefore, the
order of reactivity of alkyl halide is RI > RBr > RCl >RF.
Nature of the solvent
Polar protic (e.g. alcohols, water etc.) favor SN1 mechanism.
[Link]@[Link]
SN1 SN2
[Link] is Unimolecular (or depends only upon 1. Molecularity is Bimolecular (Substrate and nucleophile)
Substrate).
[Link] is governed by the stability of Carbocation. [Link] hindrance is the prime factor for reactivity.

[Link] halides favor SN1 mechanism in the order as: [Link] halides favor SN2 mechanism in the order as:
3o > 20 ≫ 10. 10 > 2 0 > 3 0

[Link] (generally neutral) nucleophile prefers this [Link] (generally) bearing a negative charge)
reaction. nucleophile prefers this mechanism.
[Link] protic (e.g. alcohols) solvents are required. [Link] aprotic (e.g. DMSO, acetone) is required.

[Link] or retention and inversion in products will be [Link] inversion product will be formed.
obtained.
[Link] is a two-step mechanism. [Link] is only a single step mechanism.
[Link] is formed as an intermediate part of the [Link] carbocation is formed during the reaction.
reaction.
[Link] is no partial bond formed with the carbon [Link] forms a partial bond with the nucleophile and
during this reaction. the leaving group.
[Link] are many steps in this reaction which start [Link] process takes place in only one cycle, with a single
with the removal of the group while attacking the intermediate stage.
nucleophile. [Link]@[Link]
ELIMINATION REACTION
When alkyl halides are heated with an alcoholic solution of KOH or NaOH, an alkene will be formed by the
elimination of a molecule of hydrogen halide and the process is known as dehydrohalogenation.

More Examples: H Br

H3C C CH2 [Link] H3C C CH2 KBr H2O


H H
1-Bromopropane Propene
CH3 CH3

H3C C Br [Link] H3C C CH2 KBr H2O


2-methylpropene
CH3

2-bromo-2-methylpropane

This dehydrohalogenation reaction is also known as 1,2 – elimination reaction


which involves the loss of Hydrogen atom from 𝛼 - Carbon atom and loss of
Hydrogen atom from 𝛽 – Carbon atom according to Saytzeff rule.
[Link]@[Link]
SAYTZEFF RULE:
The rule formulated in 1875 by a Russian chemist (University of Kazan) Alexander Saytzeff to give idea about main
product is Saytzeff rule.
This rule is stated as – ‘The preferred product is the alkene that has the greater number of alkyl groups
attached to the doubly bonded carbon atoms or highly branched and highly symmetrical alkene is the major
products in dehydrohalogenation process.’ Br
H2 [Link],
H3 C C C CH3 H3C C C CH3 H3C CH2 C CH2
H H H H
2-Bromobutane ([Link] bromide) 2-butene (81%) 1-butene (19 %)

Two broad categories of elimination reactions as proposed by Huges and


Ingold have been recognized as follows: -
E2 REACTION
Bimolecular Elimination reaction is known as E2 reaction. When alkyl halide is
heated with a strong base, such as hydroxide ion (OH-) or alkoxide ion (RO-), it
gives an alkene by dehydrohalogenation (α,β – elimination).
H2 [Link],
H3C C Br H 2C CH2 KBr H2O
Bromoethane Ethene
[Link]@[Link]
KINETICS
It is single step reaction but the rate of E2 reactions depends upon the concentration of both
alkyl halide and base and therefore its rate is proportional to the concentration of both reactants
and it follows second order kinetics.
R ∝ [Alkyl halide] [Base]
R = [RX] [: B]
It is bimolecular because two molecules undergo covalency changes in the rate determining
step.
MECHANISM
Like SN2 reaction mechanism, the E2 mechanism is a one step process or concerted process which
proceeds through a transition state where bonds are partially formed and broken to form with the removal
of Hydrogen and Halogen at the same time.
B: H
B H
C C C C C B H X
C

X X
Transition State An Alkene
Alkyl halide (Substrate)
The base (: B) pulls proton away from a neighboring Carbon, halide ion
departs simultaneously and double bond is formed. [Link]@[Link]
STEREOCHEMISTRY
E2 reaction mechanism should be occurred with a periplanar geometry (all
four reacting atoms – the hydrogen, the two carbons and the leaving group
lie in the same plane).
B: B H
H
C C C C
C C B H X
X
X

In this reactions, Syn periplanar geometry in which the H and X are on the
same side of the molecule and anti-periplanar geometry in which the H and
X are on the opposite side of the molecule are possible.

[Link]@[Link]
ORIENTATION
The orientation is strongly according to Saytzeff rule.
Br
H2 [Link],
H3C C C CH3 H3C C C CH3 H3C CH2 C CH2
H H H H
2-Chlorobutane ([Link] bromide) 2-butene (81%) 1-butene (19 %)

Here, 2-butene is disubstituted and 1-butene is monosubstituted, so more


substituted alkene is preferred according to Saytzeff rule.
REACTIVITY
The decreasing order of reactivity alkyl halide towards dehydrohalogenation reaction is:
Tert. Alkyl halides (3°) > Sec. Alkyl halides (2°) > Primary Alkyl halides (1°)
Reactivity of alkyl halides for elimination or dehydrohalogenation (E2) reaction depends on number of 𝛽-
hydrogen atoms. As the branching in alkyl halide increases, then (a) number of 𝛽- hydrogen atoms for
attack by base will be increased so that probability factor towards elimination becomes favourable and (b)
more highly branched or more stable alkene with more stable transition state and lower Eact will be formed.
[Link]@[Link]
FACTORS AFFECTING THE RATE OF E2 REACTIONS
1. Nature of the substrate- With increase in 𝛼 – and 𝛽 – branching in haloalkane (or the
substrate), the rate of E2 reaction increases since the stability of transition state is increased with
branching and increase in number of alkyl or aryl groups on the C-atom where the chance of
formation of double bond.
2. Strength and Concentration of Base- Rate of E2 reactions are increased with increasing
strength and concentration of the added base.
The order of strength of bases is: 𝑁𝐻2− > 𝑂𝐸𝑡 − > 𝑂𝐻 −
Also, the order of E2 reactions on a given substrate under identical conditions is also found to be:
𝑁𝐻2− > 𝑂𝐸𝑡 − > 𝑂𝐻 −
3. The nature of the leaving group- The rate of E2 reaction is higher if the leaving group is better
and ability of leaving group is better if size is increased (increasing size of Halogen atoms). The
order of reactivity of different haloalkanes towards E2 reaction is:
RI > RBr > RCl > RF
Also, C-I bond has the minimum bond dissociation energy and can be broken most easily and
hence alkyl iodide has the maximum stability.
4. The nature of solvent- Less polar solvents are favourable for E2 reaction that increases the
yield of E2 reaction product.
5. Effect of Temperature- The rate of E2 reactions is increased with the increase in temperature.
[Link]@[Link]
E1 REACTION
Elimination unimolecular reaction is known as E1 reaction. This reaction is particularly
common in tertiary halides and takes place in the absence of a strong base. When 2-
methyl propane is heated with aqueous ethanol at 25℃, it gives 2-methyl propene by
dehydrohalogenation (α,β – elimination).

CH3 CH3

[Link],
H3C C Br H3C C CH2

2-methyl propene
CH3 (Isobutylene)
2-Bromo-2-methyl propane

KINETICS
It is two step reaction but the rate of E1 reactions depends only upon the concentration of alkyl halide or
the substrate and is independent of the concentration of base and therefore its rate is proportional to the
concentration of reactants and it follows first order kinetics.
R ∝ [Alkyl halide]
R = [RX]
It is unimolecular because one molecules or alkyl halide only undergo covalency changes in the rate
determining step or in first step. [Link]@[Link]
MECHANISM
Like SN1 reaction mechanism, the E1 mechanism is a two-step process or not-concerted
process as follows:
Step I: Generation of Carbocation- It is a slow and rate determining step in which
heterolysis of alkyl halides to form carbocation and halide ion as:
Br

Slow
H 3C C C H3C C C X
r.d.s.
CH3 H CH3 H
2-Bromo-2-methyl propane (Carbocation)

Step II: Abstraction of Proton by Base-


(Carbocation is rearranged to give more stable carbocation if necessary.)
In this step, base abstracts proton of adjacent carbon from carbocation to give
alkene.
Fast
H3C C C H3C C C H:B
:B
CH3 H CH3
(Carbocation) (Alkene)

[Link]@[Link]
ORIENTATION
The orientation of E1 reaction mechanism is strongly according to Saytzeff rule.
CH3 CH3 CH3
H2 [Link], H2
H3 C C C CH3 H3C C C CH3 H3C C C CH2
H

Br 2-methyl-2-butene (71 %) 2-methyl-1-butene (29 %)


3-Bromo-2-methyl butane

Here, 2-methyl-2-butene is highly branched or symmetrical than 2-methyl-


1-butene and is the major product in accordance with the Saytzeff rule.
STEREOCHEMISTRY
E1 reaction mechanism not required any geometric requirements because the halide and
hydrogen are lost in two separate steps.
REACTIVITY
The decreasing order of reactivity alkyl halide towards dehydrohalogenation reaction is:
Tert. Alkyl halides (3°) > Sec. Alkyl halides (2°) > Primary Alkyl halides (1°)
Reactivity of alkyl halides for elimination or dehydrohalogenation (E1) reaction depends on stability of carbocation
formed in the step I. A tertiary carbonium ion has maximum stability followed by secondary and followed by primary
carbonium ion. Also, order of reactivity with different halogens with a given alkyl group is: I > Br > Cl > F, same as in
E2 reactions. [Link]@[Link]
FACTORS AFFECTING THE RATE OF E1 REACTIONS
1. Nature of the substrate- The substrate which can form most stable tertiary
carbonium ion is the most reactive since, carbonium ion is the intermediate formed in E1
mechanism and rate of reaction is controlled with the stability of carbocation formed.
2. Strength and Concentration of Base- Rate of E1 reactions are not altered with the
concentration and strength of added base.
[Link] nature of the leaving group- The rate of E1 reaction is faster if the leaving group
is best and the best leaving group are those which are more polarizable and are least
basic. The order of reactivity of different leaving groups towards E1 reaction is:
H2O > ROH > 𝐶𝐻3𝐶𝑂𝑂 − > 𝑂𝐻 − > 𝐼 − > 𝐵𝑟 − > 𝐶𝑙 − > 𝐹 −
[Link] nature of solvent- Highly polar solvents are favourable for E1 reaction that
increases the yield of E1 reaction product because E1 reactions involves with the
carbocation intermediates and rate is increased with increasing polarity of solvents.
Hydroxylic solvents of low polarity and poor nucleophilicity favor E1 reactions.
[Link] of Temperature- The rate of E1 reactions is increased with the increase in
temperature.
[Link]@[Link]
E2 Reaction E1 Reaction
It is bimolecular and follows second order It is unimolecular and follows first order kinetics.
kinetics. Thus, R = [RX]
Thus, R = [RX] [: B]
This reaction is a single step process or a This reaction is two-step process or a non-
concerted process. concerted process.
No intermediate is formed or proceeds with Intermediate or carbocation is formed in the first
the formation of transition state. step.

Due to the greater stability of the more Due to the greater stability of the carbocation
highly branched alkenes being formed, being formed in the first step, reactivity of E1
reactivity of E2 reactions increases as: 1° < 2° reactions increases as: 1° < 2° < 3°
< 3°.

It is dependent to the High concentration of It is independent to the concentration of base.


strong base. No good base or nucleophile (week base is also
sufficient).

Formation of co-planar bimolecular Formation of carbocation is the r.d.s.


transition state is the r.d.s.

Aprotic polar solvent (not important) favor protic polar solvent favor for this reaction.
for this reaction. [Link]@[Link]
MARKOVNIKOV’S RULE OF ELECTROPHILIC ADDITION TO UNSYMMETRICAL ALKENE
The rule propounded by a Russian chemist Vladimir Markovnikov in 1869 to give idea about electrophilic
addition to unsymmetrical alkene.
Statement – ‘When an unsymmetrical reagent (HX, H2SO4 etc.) adds to an unsymmetrical compound
or molecule (Alkenes), the electropositive part of the regent becomes attached to the multiple
bonded carbon which bears greater number of hydrogen atoms attached to it.’
Br Br

H3C C CH2 HBr H3C CH CH3 H3C CH2 CH2


H
Propene 2-bromopropane 1-bromopropane
(Markovnikov's Product)

The reaction where one direction of a reaction is selective or preferred than


other is called Regioselective reaction. Markovnikov’s orientation is one of
the most common examples of Regioselective reaction (Latin; Regio =
direction) since only one of possible isomeric products is exclusively or
nearly exclusively formed.

[Link]@[Link]
Examples:
ADDITION TO UNSYMMETRICAL ALKENES
Addition of a hydrogen halide to an unsymmetrical alkene gives two
possible products but product is according to Markovnikov’s orientation.
Br Br

H3C C CH2 HBr H3C CH CH3 H3C CH2 CH2


H
Propene 2-bromopropane 1-bromopropane
(Markovnikov's Product)

I I

H
H3C C CH2 HI H3C C CH3 H3C C CH2

CH3 CH3 CH3


2-methyl propene
(Isobutylene) 2-iodo-2-methyl propane 1-iodo-2-methyl
(Markovnikov's Product) propane

[Link]@[Link]
MECHANISM
It is an example of electrophilic addition reaction and this reaction occurs with following two steps as in
symmetrical alkenes: -
Step I: π – electrons of unsymmetrical alkenes form a bond with a proton from hydrogen halide to
form more stable carbocation and a halide ion. It is a slow rate determining step-
Slow H2 Slow H X
H3C C CH2 H X H3C C CH2 X H3C C CH2 H X H3C C CH3
H OR, H
Propene Primary Carbocation Halide ion Propene Halide ion
Secondary Carbocation
(less stable) (more stable)

Here, more stable secondary carbocation predominates since it is formed faster due to
lower energy of activation.
Step II: Nucleophilic attack by halide ion to more stable carbocation to form alkyl
halide- X But,
H2 Fast H2 H2
X H3C C CH2 H3C C C X H Fast
X H3C C CH3 H3C C CH3
H
1-halopropane
Nucleophile (minor product)
Nucleophile 2-halopropane
(major product)
Here, the product is in accordance with the Markovnikov’s rule.
[Link]@[Link]
ADDITION OF HYDROGEN BROMIDE (PEROXIDE EFFECT)
When hydrogen bromide (HBr) is added to unsymmetrical alkene in presence of organic peroxide such as R-O-O-R,
Ar-O-O-Ar, Ar-CO-O-O-CO-Ar etc., the direction of addition is exactly reversed or minor product according to
anti-Markovnikov’s rule or peroxide
Markovnikov’s rule will be obtained. This is known as
effect or Kharasch’s effect. This is also an example of Regioselective reaction.
Br Br

R-O-O-R
H3C C CH2 HBr H3C CH2 CH2 H3C CH CH3
H
1-bromopropane 2-bromopropane
Propene
anti-Markovnikov's product

Br Br
R-O-O-R H
H3C C CH2 HBr H3C C CH2 H3C C CH3

CH3 CH3 CH3


2-methyl propene
(Isobutylene) 1-iodo-2-methyl propane 2-iodo-2-methyl propane
anti-Markovnikov's product
This is experimented by two American chemists M. S. Kharasch and F. R.
Mayo of Chicago University in 1933.
They also found that peroxide effect of HBr to alkenes can be prevented by
the addition of certain inhibitors like hydroquinone or Diphenyl amine.
[Link]@[Link]
MECHANISM
It is an example of free radical addition reaction mechanism and this reaction occurs with following steps: -
Chain initiation step-
Peroxide gets dissociated at first to give free alkoxy radicals that attack HBr to form bromine free radical.

Homolysis
RO OR 2 RO
Alkoxy free radical
Homolysis
RO H Br ROH Br
Chain Propagation step-
Bromine free radical then attacks to the alkene molecule giving two possible
bromo-alkyl free radicals. Br
Br

H3C C CH2 Br
OR, H3C C
H
CH2 Br H3C C
H
CH2

H H3C CH CH2 Propene Primary Free radical


Secondary free radical (less Stable)
Propene
(More Stable)
But the more stable radical then reacts with HBr to give anti-Markovnikov’s product and another bromine
free radical which further propagates the chain reactions.
Br
Br

H3C CH2 CH2 Br


H3C CH CH2 H Br
1-bromopropane
anti-Markovnikov's product

Secondary free radical


(More Stable) [Link]@[Link]
HCl and HI do not give Kharasch peroxide effect because:
i. The H-Cl bond (103 Kcal/ mole) is stronger than H-Br bond (87
Kcal/ mole) which is not broken by the alkoxy free radicals
obtained from peroxides.
ii. The H-I bond (71 Kcal/ mole) is weaker than H-Br bond (87
Kcal/ mole) which is not broken by the alkoxy free radicals
obtained from peroxides.
But the iodine atoms so formed readily combine with each other to
give iodine molecules, rather than attack the double bond alkenes.

[Link]@[Link]
Re-arrangement Reactions
The reactions that are accompanied by changes in carbon skeleton of the molecule are
termed as rearrangement reactions. In rearrangement reaction there is migration of
group from one atom to another atom. Migration origin is the atom from where the group
migrates. Migration terminus is the atom where the group links itself. The migrating
group migrates with its pair of electrons or without its pair of electrons. Generally, this
migration is l, 2-shift. During the migration the migrating group may completely detach
from original molecule (intermolecular rearrangement) or may not detach and remains
in same molecule (intramolecular rearrangement).
In most of the rearrangement the migrating group migrates along with its pair of electrons
to electron deficient C, N or O.

The molecular rearrangements are defined as reactions which involve changes in the relative positions of atoms and
bonds resulting in the change of molecular skeleton. [Link]@[Link]
Fries Rearrangement Reactions

Beckmann Rearrangement Reactions

[Link]@[Link]

You might also like