Programme Code- MSCCH-17/18/19

Course Code-CHE- 502

Block – 2: Organic reaction mechanism

Lecture-3

Presented by-
Dr. Charu C. Pant
Department of Chemistry
Uttarakhand Open University, Haldwani
 LEARNING OUTCOMES
After studying this Chapter, you shall be able to:
To know about electronic effect and its types
inductive effects
Classify a group into +I or –I group
Understand mesomeric or resonance effect
Applications of Electronic Effects
To Know about aromaticity
Be familiar with the terms aromatic and anti-aromatic
Classify any organic compound into aromatic, anti-aromatic and
aliphatic (or non- aromatic)
To know about Resonance, Conjugation and Cross Conjugation
 INTRODUCTION:
You are already familiar with various electronic effects. But to
understand the properties of organic molecules, like acidity, basicity,
stability of various species, and to understand the organic reactions and
their mechanism, it is very important that we revisit the electronic effects
operating especially with a detailed study of conjugated chemical
bonding.
During most of the organic reactions, reagents either undergo heterolysis
to give rise to electrophiles and/ or nucleophiles; or they undergo
homolysis to give rise to free radicals. Electrophiles being electron
deficient search for electron rich site in the organic substrate to attack
and form the bond. But, if there are more than one electron rich sites in
the organic substrate, the electrophile obviously would prefer to attack
on the most electron rich site. On the other hand, nucleophiles being
electron rich, search for electron deficient sites in the organic substrate.
 Types of Electronic Effects:
There are four types of electronic effects mainly, viz. inductive effect,
mesomeric (or resonance) effect, electromeric effect and
hyperconjugative effect. Of these, electromeric effect is temporary while
rest is permanent and is exhibited as the dipole moment of the molecule.
1. Inductive effect:
In general, a covalent bond between two atoms must share the pair of
electrons equally. If the electronegativities of the two atoms are different,
this sharing of electrons is not equal and the more electronegative atom
gets a fractional negative charge due to the greater attraction of the
shared pair of electrons towards itself and the other atom gets a fractional
positive charge. Fractional or partial negative charge is represented by d-
(pronounced as delta minus) and Fractional or partial positive charge is
represented by d+ (pronounced as delta plus), d signifying the very less
magnitude of charge.
For example, C - X (X = halogen) bond is polar with C having a d+
charge and the halogen having a d- charge. The magnitude or value of
these fractional charges increases with an increase in the
electronegativity of the halogen i.e. for halogens, it is in the order F > Cl
> Br > I.
Here, C1 acquires slight positive charge (d+) due to the electronegativity
of Cl which in turn acquires slight negative charge (d-). C1 thus becomes
electron deficient and it exerts a pull on the electrons forming covalent
bond between C1 and C2 but less strongly. As a result, C2 acquires a
lesser positive charge (dd+) as that on C1. C3 similarly acquires even
lesser positive charge (ddd+) and so on. Thus a polarity is slowly
induced throughout the carbon chain.
However, the effect is very very less beyond carbon 3 or 4. In other
words, the effect diminishes as one moves further in the carbon chain
relative to the position of the group. The phenomenon of transmission of
charge arising due to electronegativity difference in a covalent bond (i.e.
dipole) through a chain of carbon atoms linked by sigma bonds is called
inductive effect.
 Types of Inductive effect:
1. -I Effect: The atoms/groups like Cl which are more electronegative
than carbon gain a slight negative charge on them and withdraw the
electrons of the carbon chain towards themselves are known to exert -
I Effect (pronounced as “minus I effect”).
2. +I Effect: The atoms/groups which are more electropositive than
carbon gain a slight positive charge on them and push the electrons of
the carbon chain away from themselves are known to exert +I Effect
(pronounced as “plus I effect”)
 Characteristics of Inductive effect:
1. It is a permanent effect.
2. It operates through sigma bonds. (Note that all the single, double and
triple bonds have a sigma bond in them.)
3. Its magnitude goes on decreasing with increase in distance from the
atom/group responsible for the same. Inductive effect is almost
negligible after the third or fourth atom.
-I effect of some groups is in the order:
-H < -C6H5 < -OCH3 < -OH < -I < -Br < -Cl < -F < -COOH < -CN < -
NO2 < -N+(CH3)3
+I effect of some of the groups is in the following order:
H- < D- < -CH3 < -CH2R < CHR2 < -CR3 < -COO-
 Types of +M/+R Effect :
The atoms/groups like Cl in which lone pair(or electrons of negative
charge) is in conjugation with double or triple bond are electron
donating and gain a formal positive chargein the resonating structure in
the process and are known to exert +M/+R Effect.
For example in the following case, the Cl is not conjugated to the double
bond and hence in the following molecule, Cl is exerting its only –I
effect.
H2C=CH-CH2-Cl
 -M/-R Effect:
The atoms/groups like –NO2 which are in conjugation with double or
triple bond and are electron withdrawing and gain a formal negative
charge in the resonating structure in the process and are known to exert –
M/-R Effect:
Consider the case of –NO2 joined to a conjugated system, where the nitro
withdraws the conjugated electrons and gives rise to polarization as shown
below
 Applications of Electronic Effects:
There are three permanent effects, in most cases, the dominant one is
mesomeric effect, followed by hyperconjugative and then inductive
effect. One important exception is that in case of halogens attached to
conjugated systems like benzene, -I is more dominant than +M. These
electronic effects have a very vast application and impact on the various
properties of the organic molecules/species. Let us try to understand
effects of these electronic effects on the stability of carbon intermediates,
effect on acidity and basicity.
1. Effect on Stability of carbon intermediates:
In order to understand the stability of any charged species, keep in mind
that more is the delocalization of the charge, greater is the stability.
Electron donating groups (+I, +M and +H) hence, stabilize electron
deficient species like carbocation and free-radicals. On the other hand,
Electron wthdrawing groups (-I and -M ) hence, stabilize electron rich
species i.e, carbanions.
a. Stability of carbocations:
The carbocations are generally unstable due to electron deficiency at the
positively charged carbon atom but any effect which decreases the
positive charge on this carbon increases their stability. This order of their
relative stability is
This can be explained as follows. The +I effect of the alkyl group pushes
two electrons towards the electron deficient carbon which may be
summarised as 1o < 2o < 3o. However carbocations like allyl and benzyl
are stable due to resonance.
Thus,

2. Stability of carbanions:
The carbanions are unstable due to a negative charge on carbon and any
factor which increases this negative charge makes them more unstable.
Therefore, the groups with +I effect decreases their stability.
Hence the order of their relative stability is the reverse of carbonium ions
and is as follows:

Due to the destabilizing +I effect of alkyl groups. However, allyl and

benzyl carbanions are as usual more stable due to resonance. Thus,
3. Stability of carbon free radicals:
Free radicals are unstable due to unpaired electron and electron
deficiency at the carbon atom and electron donating effect increases their
stability. This order of their relative stability is

This is due to the increase in the number of +I effect of the alkyl group.
This order may be summarised as 1o < 2o < 3o.
However carbon free radicals like allyl and benzyl are stable due to
resonance. Thus,
Allyl and benzyl carbocations have greater stability than tertiary,
secondary and primary free radicals .. Thus the overall stability is in the
following order:
4. Effect on Acidity:
In a molecule having an electronegative atom joined directly to H atom,
the acidity is affected by the following two factors:

1.Ease of Deprotonation:
Higher the electronegativity of the electronegative atom, higher is the
acidity. The higher electronegativity ensures easy deprotonation.
2. Stability of conjugate base (or the ion being formed): The
conjugate base must be stable. Higher electronegativity helps in the
stability of the anion. Both these conditions are enhanced by introducing
electron withdrawing groups (-M, -H or –I) and decreased by electron
donating groups (+I, +M, +H) .
Remember that the second condition is more dominant one than the first
to arrive to the conclusion. Hence if two are opposing, rely on the second
one.
e.g., Comparison of acidity of phenol, and o, m & p-nitrophenols
First of all identify the differentiating groups amongst all. In the
framework of phenol, the nitro groups at different positions are
differentiating groups, which are responsible for different acidities of
these molecules. Write the effect that they are exerting as depicted below.
 Aromaticity:
You are already aware that the aromatic compounds apparently contain
alternate double and single bonds in a cyclic structure and resemble
benzene in chemical behaviour. They undergo substitution rather than
addition reactions. This characteristic behaviour is known aromaticity.
criteria of aromaticity:
Following are the main criteria of aromaticity:
1. Chemical behavior: electrophilic aromatic substitution.
2. Structural: bond length equalization due to cyclic delocalization.
3. Energetic: enhanced stability (large resonance energy).
4. Magnetic: "ring current" effects.
a) anomalous chemical shifts in NMR.
 b. large magnetic anisotropies
c. high diamagnetic susceptibility.
Let us begin with recalling the criteria for classifying any compound as
aromatic, anti-aromatic and aliphatic or non-aromatic by examining its
structure, i.e., by Huckel’s rule.
Huckel’s Rule and aromaticity:
A molecule is aromatic if all the following conditions are fulfilled:
It is cyclic, planar and has continuous delocalization of p electrons
(electrons in p orbitals) with or without the participation of lone pair(s)/-
charge/ + charge (i.e having electrons or vacant p orbital).
The delocalised p-electron cloud must contain a total of (4n+2)p
electrons, where n is a whole number (i.e., n =0,1,2,3 and so on).
Putting n= 0 in (4n+2)p we get 2p electrons, similarly putting n=1, we
get 6p electrons; n= 2 gives 10p electrons; n= 3 gives 14p electrons and
so on.
So whenever a cyclic, planar and (4n+2)p electrons are continuously
delocalized, it leads to the extra stability of the molecule referred to as
aromaticity. On the other hand, whenever a cyclic, planar and (4n)p
electrons are continuously delocalized, it leads to the extra destability of
the molecule referred to as anti-aromaticity. When either the molecule
is not cyclic or is not planar or the continuous delocalization of p
electrons is not there, the molecule is aliphatic or non- aromatic.
In other words,
• If first condition is fulfilled and if in the second condition there are
(4n+2)p electrons, it is aromatic.
• If first condition is fulfilled and if in the second condition there are 4n p
electrons, it is anti-aromatic.
•If the first condition is not fully met, it is aliphatic, the second condition
need not be looked at all.
The term non-aromatic is applicable to both aliphatic as well as anti-
aromatic.
Of these the stability is in the order :Aromatic > Aliphatic > Anti-
aromatic
Condition for Aliphatic or Aromatic Anti-aromatic
Aromaticity Non- aromatic
1. Cyclic, planar and Not fulfilled Fulfill the Fulfill the
continuous ( X) first first
delocalization of Condition Condition
p electrons
(Yes) (Yes )

(4n+2)p
No need to look
(4n)p electrons
2. (4n+2)p electrons for this condition Electrons
(yes) (4n+2)p
if first condition is
requirement not
not fulfilled
fulfilled ( No )
( No)
Let us consider some examples to apply these conditions.
1. Three membered cyclic species:
2. Five membered cyclic species:
3. Six membered cyclic species:

4. Seven membered cyclic species:

•Fused polynuclear hydrocarbons:
Naphthalene and azulene have 10p electrons each, Anthracene has 14p
electrons. All of them satisfy both the conditions and hence are aromatic.
 Resonance:
Most covalent molecules have a unique Lewis formula (dot structure).
These Lewis formula explain the bonding in that molecule, but for many
molecules, two or more dot structures are feasible, rather than only one
structure. The phenomenon of resonance was put forward by Heisenberg
to explain the properties of such covalent molecules/species that could
not be represented by a single structure.
For example, the formate ion can be represented by two equivalent
structures, (a) and (b), as shown below:
O O

H C H C

O
O (b )
(a )
Characteristics of Resonance/Resonance Structures
1.Resonance exists only in those parts of molecules that are composed of
sp or sp2 atoms; p orbitals are an absolute requirement for resonance.
Hence it does not occur in sp3 hybridised atoms.
2.All the atoms in the molecules taking part in resonance should be
coplanar. This is necessary for effective overlap of the p orbitals.
3.While making a resonance structure from other, electrons move
between adjacent atoms. Type of electrons that can be moved are lone
pairs or л electrons (or a negative charge) or the unpaired electron
present on radicals. These electrons reside on a ‘resonance donor atom’
and move to the ‘resonance acceptor atom’ which must be adjacent to
the donor atom. The acceptor atoms must also have an open octet, be
able to or have another electron pair (lone pair or л electrons) that can be
displaced. An atom with a formal positive charge, can also be a
resonance acceptor atom, as long as the atom does not accept more
electrons than it can normally accommodate.
4. The resonance structures (or contributing structures) do not have real
existence as individual species. These are only imaginary structures,
proposed to explain the properties of the molecule. None of these
‘resonance structures’ can be prepared in the laboratory. In real sense, the
resonance hybrid is the real structure. Due to the resonance phenomenon,
the bond lengths in resonating structures exhibit equal values, i.e become
equal.
For example, in case of benzene, in the resonance hybrid structure , the
C-C bonds are not alternate single and double bonds, rather all of them
are intermediates of single and double bonds and the bond lengths are
equal.

Resonance hybrid

The resonance hybrid has lower energy and thus greater stability than
any of the contributing structures. Also, greater the resonance energy,
greater is the stability of the molecule.
Examples:
 Conjugation:
Conjugation is the overlap of one p-orbital with another across an
intervening sigma bond (in larger atoms d-orbitals can be involved). In
molecules that contain more than one multiple bond,
e.g. dienes with two C=C bonds, it is found that compounds in which the
bonds are conjugated (alternating multiple and single bonds) are slightly
more stable than those in which they are isolated.
For example, out of the following dienes, the conjugated one (I) is more
stable than (I).
Base
Catalyst
Examples:
The atoms that form part of a conjugated system in the examples below
are shown in blue, and the ones that do not are shown in red. Notice that,
it is sp3 hybridized atoms that break a conjugated system.

Conjugation system

Cross-conjugation:
Cross-conjugation is a special type of conjugation in a molecule. Here,
out of a set of three л bonds only two interact with each other by
conjugation, while the third one is excluded from interaction. A cross-
conjugated system has a double-bonded unit single-bonded to one of the
middle atoms of another conjugated chain. On the other hand, a normal
conjugated system such as a polyene typically has alternating single and
double bonds along consecutive atoms.
R R

R C R

C C C
R C C R

R R

In other words, one of the double-bonds branches off rather than

continuing consecutively. Hence, the main chain is conjugated, and part
of that same main chain is conjugated with the side group, but all parts
are not conjugated together.
This type of conjugation has an impact on reactivity and molecular
electronic transitions.
Examples:
1. Simple cases:

B enzophenone D ivinyl ketone p -Q uinone

 Comparison of conjugation, cross-conjugation and non-
conjugation
Conjugation comes in three “flavors,” the simplest of which is the
normal straight-through (linear) conjugation seen in many biomolecules
(such as Vitamin A).

However, it is possible for two systems to be in “cross-conjugation” with

each other, as in the example below (the two benzene rings are cross-
conjugated, NOT conjugated!):
Conjugation is broken completely by the introduction of saturated (sp3)
carbon: There are a lot of double bonds, but there is NO conjugation in
this molecule.