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ELECTRONICEFFECTS, ACID-BASESTRENGTH
ANDREACTIONINTERMEDIATES
1. Electronic effects :
The effect which appears due to electronic distribution is called electronic effect.
Classification :
1.1 Inductive Effect
1.1.1 The normal CC bond has no polarity as two atoms of same electronegativity (EN) value are connected to
each other. Hence the bond is nonpolar. Consider a carbon chain in 1-chloro butane, Here due to more ENof
Cl atom C Cl bond pair is slightly displaced towards Cl atom hence creating partial negative (o ) charge
over Cl atom and partial positive (o+) charge over C
1
atom.
Now since C
1
is slightly positive, it will also cause shifting of C
1
C
2
bond pair electrons towards itself
causing C
2
to acquire small positive charge. Similarly C
3
acquires slightly positive chargecreating an induction
of charge in carbon chain. Such an effect is called inductive effect.
Diagramshowing I effect
The arrowshows electron withdrawing nature of Cl group.
Thus inductive effect may be defined as a permanent displacement of o bond pair electrons due to
a dipole. (Polar bond)
Some important points are:
(a) It can also be defined as polarisation of one bond caused by polarisation of adjacent bond.
(b) It is also called transmission effect.
(c) It causes permanent polarisation in molecule, hence it is a permanent effect
(d) The displacement of electrons takes place due to difference in electronegativity of the two atoms involved
in the covalent bond.
(e) The electrons never leave their original atomic orbital.
(f) Its magnitude decreases with distance and it is almost negligible after 3rd carbon atom.
(g) The inductive effect is always operative through o bond, does not involve t bond electron.
1.1.2 Types of inductive effect :
(a) I Effect : The group which withdraws electron cloud is known as I group and its effect is called
I effect. Various groups are listed in their decreasing I strength as follows.
> > > NO
2
> SO
2
R > CN > CHO > COOH > F > Cl >
Br > I > OR > OH > C CH > NH
2
> C
6
H
5
> CH = CH
2
> H.
(b) + I effect : The group which release electron cloud is known as + I group and effect + I effect.
> > C(CH
3
)
3
> CH (CH
3
)
2
> CH
2
CH
3
> CH
3
> D > H
The hydrogen atom is reference for + I and I series. The inductive effect of hydrogen is
assumed to be zero.
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Ex.1 Since NO
2
is I group it pulls or withdraws electron from cyclohexane ring making it electron deficient
Let us consider effect of COOH & COO

in carbon chain
Ex.2
Ex.3
Due to e donating nature of carbon chain has become partially negative but COOH is I group
therefore carbon chain has become partially positive.
Ex.4 (a) CH
3
CH
2
CH
2
(b)
(c) CH
2
N C

(d)
(e) (f)
(g) (h)
(i)
1.1.3 Applications of Inductive effect :
(a) In deciding acidic strength of aliphatic carboxylic acids.
I effect Acidic strength (presence of I groups increases acidic character)
+ I effect Basic strength (presence of + I groups increases basic character)
The Bronsted - Lowry Definition of Acids and Bases
According to the Bronsted - Lowry theory : An acid is a substance that can donate (or loose) a proton,
and a base is a substance that can accept a proton.
Acidic strength is directlyrelated to stability of conjugate base I stabilises conjugate base amd +I destabilises
conjugate base.
Ex.5 (I)
Cl
|
COOH CH C H C H C H
2 2 3

(II)
Cl
|
COOH CH CH CH CH
2 2 3

(III)
Cl
|
COOH CH CH CH CH
2 2 3

(IV) CH
3
CH
2
CH
2
CH
2
COOH
IV III II I > > >
order strength Acid
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Explanation : We know that I effect increases acidic strength. But it is distance dependent effect so
where the I group is nearest to COOH, It exert strong effect and makes acid stronger.
Ex.6 (I) O
2
N CH
2
COOH (II) F CH
2
COOH
(III) H
3
CO CH
2
COOH (IV) CH
3
CH
2
COOH
IV III II I > > >
order strength Acid
Explanation : Since NO
2
has strong I effect its influence will make corresponding acid strongest ( I effect
acid character).
(b) Acidic Character of Alcohol : Greater - I effect results in greater acidic character. Similarly greater +
I effect lowers acidic character.
Ex.7 (a) Acidity : CH
2
OH < CH
2
OH < CH
2
OH < CH
2
OH
(b) Acidity : CH
3
OH > CH
3
CH
2
OH > CH OH > OH
(c) Dipole moment : Greater I effect results in greater dipole moment.
Ex.8 : CH
3
NO
2
> CH
3
COOH > CH
3
F > CH
3
OH
(d) Stability of carbocation : Carbocations are electron deficient species and they are stabilised by + I
effect and destablised by I effect. Because + I effect tends to decrease the positive charge and I effect
tends to increases the positive charge on (carbocation)
Ex.9 Stability :

3
CH < CH
3

2
CH < H C ) CH (
2 3

<

C ) CH (
3 3
(e) Stability of carbon free radical : Carbon free radical are stabilised by + I effect.
Ex.10 Stability :
-
3
CH < CH
3
-
2
CH < CH
3
< CH
3
CH
3
(f) Stability of carbanion stabilised by I effect and destabilised by +I effect.
CH
3
>
CH
3
CH
2 > CH
3
CH
2
CH
3
> CH
3
C CH
3
CH
3
1.2 Resonance & Mesomeric effect
1.2.1 Definition : Resonance is the phenomenon in which two or more structures involving in identical position of
atom, can be written for a particular species, all those possible structures are known as resonating structures
or canonical structure.
Resonating structure are only hypothetical but they all contribute to a real structure which is called resonance
hybrid. The resonance hybrid is more stable than any resonating structure. The P.E. difference between the
most stable resonating structure and resonance hybride is called resonace energy. The stability of molecule
is directly proportional to resonance energy.
Fig.1
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The most stable resonating structure contribute maximumto the resonance hybrid and less stable resonating
structure contribute minimum to resonance hybrid.
Ex.11 (I)
(II)
(III)

(IV)

(V)

(VI)

CH = CH
2
1.2.2 Resonance Hybrid :- It is the actual structure of the species without violating the rules of covalence
maxima for the atoms.

Resonance hybrid
1.2.3 Resonance Energy:- The difference in energy between the hybrid and the most stable canonical structure
is referred as the resonance energy. (as shown in Fig.2)
Fig.2
The resonance energy of a resonance hybrid is the difference between the theoritical and experimental value
of heat of hydrogenation of the compound.
Cyclohexene
+ H
2

Catalyst
+ (28.6 Kcal/mol)
Accordingly,
+ 3H
2

Catalyst
+ 3 28.6 = (85.8 Kcal/mole)
Therefore, benzene has [85.8 (49.8)] Kcal/mol less energy than expected for a typical compound with
three double bonds. Hence resonance energy of benzene molecule is 85.8 + 49.8 = 36.0 Kcal/mole.
let us see resonating structures of given molecules
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Ex.12 Write resonating structure for each of the following molecules :
(a)
3 3
CH C CH CH CH
||
O
= (a)
(b) N C CH CH
. .
N H
2

= (b)
(c) (c)
(d) CH
3
O CH = CH (d)
(e) (e)
(f) :
..
O C CH
3
=

(f)
(g) (g)
(h) (h)
(i) (i)
(j) (j)
(k) (k)
+
+
+
(l) CH
2
= C = O (l)
CH = C = O
2
. ..
.
O
O C H C
2
(m) (m)
N N N
2

1.2.3 The Rules of Resonance

(a) All the canonical forms (resonating structure) must have proper lewis structure. For instance none of
them may have a carbon atom with five bonds.
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(b) The positions of the nuclei of the atoms must remain the same in all of the structures. Structures 3
is not a resonance structure of 1 or 2, for example, because in order to formit we would have to move
a hydrogen atoms and this is not permitted :
(c) All atoms taking part in the delocalisation must lie in a plane so that orbitals overlaping become
parallel to each other.

i.e.

z
(d) All canonical forms must have the same number of unpaired electron.
(e) The energy of actual molecule is lower than of any form. Therefore delocalisation is a stabilizing
phenomenon.
(f) All canonical forms do not contribute equally to the true molecule. The more stable structure is the
greater contribution to its resonance hybrid.
1.2.4 Relative stability of the canonical form
(a) Nonpolar (uncharged) structure are most stable. Charge separation decreases stability.
Separating opposite charges requires energy. Therefore, structures in which opposite charges are
separated have greater energy (lower stability) than those that have no charge separation.
CH = CH Cl
2
CH CH = Cl
2
::
::
::+
( ) I ( ) II
(b) Structures in which all of the atoms have a complete valence shell of electrons (i.e., the noble gas
structure) are especially stable and make large contributions to the hybrid.
Ex.13 (II is more stable than I)
Ex.14 CH C = O
3
+
..
..
I
(II is more stable than I)
(c) Structures with more covalent bonds are more stable than other structures
(d) Structure that carry negative charge on a more electronegative atom and positive charge on less
electronegative atomare comparatively more stable.
Ex.15 (II is more stable than I)
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Ex.16 (I is more stable than II)
1.2.5 Mesomeric effect : Mesomeric effect is defined as permanent effect of telectron shifting frommultiple bond
to atom or from multiple bond to single bond or from lone pair to single bond.
Ex.17
I and II are resonating structures of Cl CH = CH
2
.
This effect mainly operates in conjugated system of double bond. So that this effect is also known as
conjugate effect.
Ex.18
1.2.6 Conjugation:- Agiven atom or group is said to be in conjugation with an unsaturated system if:-
(i) It is directly linked to one of the atoms of the multiple bond through a single bond.
(ii) It has bond, positive charge, negative charge, odd electron or lone pair electron.
(a) CH
2
= CH CH = CH
2
(Conjugation between C = C and C = C)
(b) CH = CH CH
2 2
+
(Conjugation between +ve charge and C= C)
(c) CH = CH NH
2 2
. .
(Conjugation between lone pair and C= C)
(d) CH
2
= CH
2
H C
-
(Conjugation between odd electron and C= C)
(e) CH = CH CH = CH CH
2 2

(Conjugation between negative charge and C= C)

1.2.7 Types of Mesomeric Effect : This is of two types
(a) + m effect (b) m effect
(a) Positive Mesomeric effect (+ m effect) : When the group donates electron to the conjugated
system it shows + m effect.
Ex.19 (I)
(II)
H C = CH CH = CH NH
2 2
. .
H C CH = CH CH = NH
2 2
- +
(III)
(IV)
(V)
(VI)
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Groups which shows '+ m' effect are :
> NH
2
> NHR > NR
2
> OH > OR >
O
||
R C NH >
O
||
R C O > Ph, CH = CH
2
> F >
Cl > Br > I, N = O.
(b) Negative Mesomeric Effect ( meffect) : When the group withdraws electron fromthe conjugated
system, it shows m effect
Groups which can show m effect are
NO
2
> C N > SO
3
H > CHO >
O
||
R C >
O
||
OH C
Ex.20
Ex.21
O N = O:
. .
+
O N O:
. .
. . +
+
O N = O:
. . +
Ex.22 H C = CH C N:
2
+
H C CH = C = N:
2 . .
Ex.23 By drawing resonating structures of following molecules, Judge whether the group attatched to ring exerts
+ m or m effect.
,
Sol. (a)
3
CH C NH
||
O
(+ m group)
NHCCH
3
O
NHCCH
3
O
NHCCH
3
O
NHCCH
3
O
NHCCH
3
O
(b) CCH
3
O
( m effect group) :
C
O CH
3
C
O CH
3
C
O CH
3 C
O
CH
3
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Note:
1. When a +m group and m group are at meta-positions with respect to each other then they are not in
conjugation with each other, but conjugation with benzene ring exists.
etc.
2. +m group increases electron density in benzene ring while m group decreases electron density in the
benzene ring.
Ex.24 Write electron density order in the following compound.
(a)
Ans. III > I > II > IV
(b)
Ans. I > II > III > IV
(c)
Ans. IV > I > III > II
1.2.8 Difference between Inductive and Mesomeric effects:-
Inductive effect Mesomeric effect
(1) It is found in saturated and unsaturated
compounds.
(1) It is found in unsaturated compounds
especially having conjugated system.
(2) It involves partial shifting of sigma
electrons.
(2) It involves complete shifting of pi-electrons
of pi-bonds or lone pair of electrons.
(3) The electron pair is slightly displaced from
its position and thus partial charges are
developed.
(3) The electron pair is completely transferred
and thus full positive and negative charges are
developed.
(4) It is transmitted over a quite short distance.
The effect becomes negligible after third atom
in the chain (distance dependent).
(4) It is transmitted from one end to other end
of the chain provided conjugation is present. It
is distance independent.
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1.2.9 Important points :
(a) If any t-bondhas more than one tbond in conjugation, then only one tbond will take part in delocalisation.
CH C CH CH
2

=
+
Out of two t bonds only one t bond will take part in delocalisation.
(b) If any conjugate position has more than one lone pair then only one lone pair will take part in the
delocalisation.
CH = CH O CH
2 3
. .
. .
+
Out of the two lone pair s only one will take part in delocalisation.
(c) If any conjugate position has t bond and any of the positive charge, negative charge, odd electron,
lone pair electrons then only t bond will take part in delocalisation.
N
. .
+
Nitrogen has t bond as well as lone pair, but only t bond of nitrogen will take part in delocalisation.
(d) Electrons of negative charge or lone pair behave as 2t electrons if it is in conjugation to t bond.
Behaves as 2t e's
C = CH NH
2
H
2
. .
Behaves as 2t e's
1.3 Hyperconjugation
1.3.1 Hyper conjugation : It is delocalisation of sigma electron with p-orbital. Also known as o t-conjugation or
no bond resonance. It may takes place in alkene, alkynes, carbocation, free radical, benzene nucleus.
Necessary Condition : Presence of at least one hydrogen at saturated carbon which is o with respect to
alkene, alkynes, carbocation, free radical, benzene nucleus.
1.3.2 Hyperconjugation in alkene
1.3.3 Hyperconjugation in carbocation
1.3.4 Hyperconjugation in radical
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1.3.5 Hyperconjugation in toluene

(a) The effect of electron displacement due to this type of resonance is called hyperconjugative effect.
(b) Since canonical forms of this resonance may not contain any bond between H and C so
hyperconjugation is also known as no bond resonance.
(c) These resonating structures only suggest that
* There is some ionic character between C H bond.
* Carbon - carbon double bond acquires some single bond character.
(d) Number of no bond resonating structures due to hyperconjugation = Number of o-hydrogens
(In aliphatic systems)
Ex.25
1.3.6 Applications of hyperconjugation
(a) Stability of Alkenes :- More is the number of hyperconjugative structures more stable is the alkene.
"More alkylated alkenes are more stable".
Stability of alkenes no. of hyperconjugative structures.
Example : 24
C = C C = CH CH
3 C = CH
2
H C
3
H C
3 H C
3
H C
3
H C
3 H C
3
CH
3
CH
3
Stability in decreasing order
(b) Heat of hydrogenation : Greater the number of o hydrogen results greater stability of alkene.
Thus greater extent of hyperconjugation results lower value of heat of hydrogenation
Stability of alkenes no. of hyperconjugative structures
ion Hydrogenat
H
1
A
Ex.26 CH
2
= CH
2
> CH
3
CH = CH
2
> CH
3
CH = CH CH
3
(AH
Hydrogenation
)
(c) Bond Length : Bond length is also affected by hyperconjugation
Ex.27

(i) Bond length of C(II) C(III) bond is less than normal CC bond.
(ii) Bond length of C(II) C(I) bond is more than normal C=C bond.
(iii) CHbond is longer than normal CHbond.
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(d) Dipole moment : Since hyperconjugation causes the development of charge, it also affects the dipole
moment of the molecule.
Ex.28 (I) CH
2
= CH
2
< CH
3
CH = CH
2
(Dipole moment)
(II) H CH = O < CH
3
< CH
3
CH = CH H (Dipole moment)
(e) Stability of carbocation : More hyperconjugation more is the stability.
Ex.29 (a) < CH
3
< CH
3
CH
3
< (CH
3
)
3
(b) CH
3
> CH
3
CH
2
CH
2
> >
CH
CH C
CH
3
3
3

(due to resultant of inductive effect and hyperconjugation)

(f) Stability of free radical : Greater the number of o-hydrogen results greater stability of carbon free radical
Ex.30 (a) < CH
3
< CH
3
CH
3
< CH
3

(b) CH
3
> CH
3
CH
2
> >
(due to resultant of inductive effect and hyperconjugation,
both operates in same direction)
2. Acids and Bases
2.1 (a) The Bronsted - Lowry Definition of Acids and Bases
According to the Bronsted - Lowry theory, an acid is a substance that can donate (or loose) a proton, and
a base is a substance that can accept a proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :
Hydrogen chloride, a very strong acid, transfers its proton to water. Water acts as a base and accepts the
proton. The products that result from this reaction are a hydronium ion (H
3
O
+
) and a chloride ion (Cl

).
The molecule or ion that forms when an acid loses its proton is called the conjugate base of that acid. (The
chloride ion is the conjugate base of HCl). The molecule or ion that is formed when a base accepts a proton
is called the conjugate acid of that base.
(b) The Lewis Definition of Acids and Bases
Lewis proposed that acids are electron pair acceptors and bases are electron pair donors. For example
aluminiumchloride, reacts with ammonia in the same way that a proton donor does. Using curved arrows to
showthe donation of the electron pair of ammonia (the Lewis base), we have the following examples:
Cl + H
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2.2 Relative acidity of hydrocarbons :
Being most electronegative the sp hybridised carbon atom of ethyne polarizes its C Hbond to the greatest
extent causing its H to be most positive therefore ethyne is most acidic hence
HC CH > H
2
C = CH
2
> H
3
C CH
3
2.3 Acidity of Phenols :
When phenol ionises the phenoxide ion is more stabilised by resonance than the unionised phenol. In phenol
unlike charges are spread and so it is less stable.
Groups which are I, m increases acidic character of phenol of effectively dispersing negative charge of
phenoxide ion.
Alternatively + I and + m groups decreases acid strength.
Ex.31
acid strength order : I > II > IV > V > III
Now
step 1, III will be least acidic as it has no dispersion of negative charge (No mesomerism).
step 2 since I, m group will increase acid strength, Nitrophenol will be most acidic followed by phenol,
step 3 Amongest cresol and methoxyphenol, methoxyphenol has +m effect of OCH
3
which increases e
density hence decrease acidic strength
Ex.32
acid strengh order : I > III > II > IV
Step 1 : Notice that CH
3
have + I effect so all methylphenols (cresols) are less acidic than phenol (I).
Step 2 : Now amongest cresols p- and o- CH
3
are increasing the e density due to their hyper conjugation
but ortho isomer has viable + I effect also, which will help in destabilising phenoxide ion therefore o- is least
acidic. Since at meta position only + I works it as least e density amongst the cresol
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Ex.33
acid strength order : II > IV > III > I
Step 1 In nitrophenols I effect of NO
2
will help to increase acidic strength hence phenol is least acidic
amongst all nitrophenols
Step 2 Only I effect is applicable in meta nitrophenol it will be number three. Now o, p have both I and
m effect of NO
2
group over OH and in this particular case para isomer is more acidic than ortho since
H is trapped by NO
2
group.
2.4 Acidity of carboxylic acids :
R C OH
O
-
R C O
O
(I)
+

H
(i)
-
R C O
O
(I) exists as two equivalent cannonical structures I(A) and I(B). This ion is resonance stablised
and resonance hybrid structure is I(C).
-
R C
O
O
I(A)
-
R C
O
O
I(B)
R C
O
O
I(C)
(ii)
-
R C O
O
ion is more stable due to resonance, hence carboxylic acids are acidic in nature.
(iii) Electron withdrawing group (I effect) stablises the anion and hence, increases acidic nature.
C
O
O
X
Ex.34 F CH
2
COOH > Cl CH
2
COOH > Br CH
2
COOH > I CH
2
COOH
Ex.35 Cl C COOH
Cl
Cl
> Cl CH COOH
Cl
> Cl CH
2
COOH > CH
3
COOH
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(iv) Electron releasing group (+ I effect) destablises the anion and hence decreases acidic nature.
C
O
O
X
Ex.36 HCOOH> CH
3
COOH> CH
3
CH
2
COOH
Ex.37
COOH
COOH
>
COOH
COOH
CH
2 >
CH
2
COOH
CH
2
COOH
Ortho effect
It is common observation that generally ortho substituted benzoic acids are highly acidic as compared to
their isomers and benzoic acids itself. This is called ortho effect in benzoic acid. However exceptions are
seen.
acid strength order : II > IV > III > I
Explanation the ortho isomer will be most acidic due to ortho effect .
Ex.38 (1) (G = m, I)
K
a
order = ortho > para > meta > benzoic acid
(2) G = (I > +m) Cl, Br, F, I
K
a
order = ortho > meta > para > benzoic acid
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(3) G = (+m > I) ..... OCH
3
K
a
order = meta ~ ortho > benzoic acid > para
(4) G = (+I, H.C.) ........ R (Alkyl group)
K
a
order = ortho > benzoic acid > meta > para
Comparison between two geometrical isomers
Ex.39 1. Maleic acid Fumaric acid
Now K
1
m
> K
1
f
Since the conjugate base is stabilised by intramolecular H bonding.
But K
2
f
> K
2
m
Since in maleate ion, after donation of two groups faces each other and
makes system unstable. In fumarate ion this repulsion is minimised.
3. BASES
3.1 Aliphatic Bases
Ease of protonation is the basic nature
Increasing strength of nitrogenous bases is related to readiness with which they are prepared to take up
protons.
Consider the following molecules
, , ,
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By visiting + I effect of methyl in above example we may expect basic nature as
NH
3
< MeNH
2
< Me
2
NH < Me
3
N (Which is not true always)
This is due the fact that basic strength of an amine in water is determined not only by ease of electron
donation (protonation) of Natombut also by the extent to which cation so formed can undergo SOLVATION
and become stabilised by H atom attatched to N atom greater is possibility of solvation via H bonding by
water. Alkyl groups are hydrophobic and inhibits H bonding hence solvation.
>
Thus, due to two opposite effect viz. solvation of cation and + I effect. The jumbled order comes to be
Me
2
NH > Me NH
2
> Me
3
N > NH
3
It is also interesting to note that in gas phase basicity order of amines follows the usual order of
Me
3
N > Me
2
NH > MeNH
2
> NH
3
Since only + I effect works and no solvation effect persists.
Similarly : On the same reasons ethyl amines and other amine follows the following order for basic strength:
Et
3
N > Et
2
NH > EtNH
2
> NH
3
(gas phase)
Et
2
NH > Et
3
N > EtNH
2
> NH
3
(water as solvent)
3.2 Aromatic amines (Ph
:
NH
2
) or Anilines :
When the lone pair lies in conjugation with a multiple bond, it resides in 2p atomic orbital, so that system
can get resonance stabilisation. Aniline is a weaker base than NH
3
because it has delocalised lone pair.
Ex.40 Which of them is strong base
In pyrole lone pairs are involved in resonacne therefore it is less basic. But in pyridine lone pairs are in
perpendicular plane of t orbitals therefore not involved in resonance
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Ex.41 Which of them is stronger base
CH
3
NH
2
Since ease of donation of lone pair of Nis basicity, CH
3
NH
2
is more basic due to + I effect of CH
3
group.
Aryl amine aniline is very less basic since lone pair of N is involved in resonance.
Steric effect of ortho-substituted group (ortho effect) :
H N:
2

G


H
H N H

G
+

H
(a) Ortho-substituted anilines are mostly weaker bases than aniline itself.
(b) Ortho-substituent causes steric hinderance to solvation in the product (conjugate acid i.e. cation).
(c) The small groups like NH
2
or OH do not experience (SIR) due to small size.
Ex.42 (1) G = (M, I); NO
2
(a) (b) (c) (d)

NH
2
(Aniline > m > p > o).
(2) G = (I); CCl
3
CCl
3

NH
2

CCl
3

NH
2

CCl
3

NH
2

NH
2
(Aniline > p > m > o).
(3) G = (I > + m); Cl
Cl

NH
2

Cl

NH
2

Cl

NH
2

NH
2
(Aniline > p > m > o)
Only (I) decides the order.
(4) G=(+I, HC); If R = CH
3
(Toluidines)
CH
3

NH
2

+I
m
CH
3

NH
2

+I
w
ating min do more HC

NH
2
(5) G = (+m > I);
K
b
order : p > Aniline > o > m
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4. Reaction Intermediate
4.1 Dissociation of a Covalent Bond :
Homolysis and Heterolysis fission of Covalent Bonds
Reactions of organic compounds always involve the making and breaking of covalent bonds. Acovalent bond
may break in two fundamentally different ways. The bond may break so that one fragment takes away both
electrons of the bond, leavingtheother fragment withanempty orbital. This kindof cleavage, calledheterolysis
(Gr: hetero-different + lysis-loosening or cleavage), produces charged fragments or ions. The bond is said to
have broken heterolytically:
The other possibility is that the bond breaks so that each fragments takes away one of the electrons of the
bond. This process, calledhomolysis (Gr. homo-thesame+lysis), produces fragments with unpaired electrons
called radicals.
Heterolysis of a bond normally requires that the bond be polarised.
Polarisation of a bond usually result from different electronegatives of the atoms joined by the bond. The
greater the difference in electronegativity, the greater the polarisation. In the given instance, atomB is more
electronegative thanA.
Even with a highly polarised bond, heterolysis rarely occurs without assistance, because heterolysis requires
separation of oppositively charged ions but oppositively charged ions attract each other, their separation
requires considerable energy. Often, heterolysis is assisted by a molecule with an unshared pair that can
form a bond to one of the atoms :
Formation of the newbond furnishes some of the energy required for the heterolysis.
4.2 Carbanion
Definition : A carbon intermediate which contain three bond pair and a negative charge on it, is called
carbanion.
Ex.43 , Methyl carbanion
Ex.44 CH
3
Ethyl carbanion
Ex.45 (CH
3
)
2
Isopropyl carbanion
Hybridisation : Hybridisation of carbanion may be sp
3
, sp
2
& sp.
Hybridisation Example
sp
3
, CH
3

sp
2
H
2
C = , CH
2
= CH
sp HC
Stability of carbanion :
Carbanions are stabilised by electron withdrawing effect as
(i) I effect (ii) m effect (iii) Delocalisation of charge
Carbanions are Lewis bases. In their reactions they seek a proton or some other positive centre to which
they can donate their electron pair and thereby neutralize their negative charge.
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CHEMISTRY
Ex.46 CH
3
>
CH
3
CH
2 > CH
3
CH
2
CH
3
>
CH
3
C CH
3
CH
3
(Stability order)
Ex.47
2
H C CH
2
CH
O
=
<
2 5 6
H C H C
O
<

3 5 6
C ) H C (
O
(Stability increasing order.)
TAUTOMERISM
Definition : Tautomerism is a phenomenon by which a single compound exists in two or more readily
interconvertible structures that differ inthe relativepositions of at least oneatomic nucleus, generally hydrogen.
Keto and Enol Tautomers
The keto and enol forms of carbonyl compounds are constitutional isomers, but of a special type, because
they are easily interconverted in the presence of traces of acids and bases, chemists use a special term to
describe this type of constitutional isomerism. Interconvertible keto and enol forms are said to be tautomers,
and their interconversion is called tautomerization.
Under most circumstances, we encounter keto - enol tautomers in a state of equilibrium. (The surfaces of
ordinary laboratory glassware are able to catalyze the interconversion and establish the equilibrium). For
simple monocarbonyl compounds such as acetone and acetaldehyde, the amount of the enol form present
at equilibriumis very small. The greater stability of the following keto forms of monocarbonyl compounds can
be related to the greater strength of the carbon-oxygen t bond compared to the carbon - carbon t bond ( ~
364 versus ~ 250 kJ mol
1
):
Keto Form Enol Form
Acetaldehyde
Acetone
Cyclohexanone
In compounds whose molecules have two carbonyl groups separated by one CH
2
group (called
|-dicarbonyl compounds), the amount of enol present at equilibrium is far higher. For example, pentane-2,
4 -dione exists in the enol form to an extent of 76% in the liquid.
The greater stability of the enol form of |-dicarbonyl compounds can be attributed to stability gained through
resonance stabilization of the conjugated double bonds and (in a cyclic form) through hydrogen bonding:
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CHEMISTRY
The conversion of a carbonyl compound into its enol is called enolization.
Lactum-Lactimsystem:
N
|
H
O
O
N
O
OH
C
||
O
SO
2
NH
C
|
OH
SO
2
N
Nitro-Acinitro system:
The acidic nature of the nitro compounds gives rise to the belief that the nitro compounds exist in two forms,
a more stable or normal nitro form and the less stable acinitro form.
R CH
2
|
N
O O
Nitroform
R CH
||
N
HO
O
Acinitroform
The stability of the nitro form as compound to the acinitro form due to stabilised by resonance.
Ex.48
C H CH N
6 5 2
O
O
Nitroform
C H CH = N
6 5
OH
O
Acinitroform
Nitroso-Isonitrososystem:
Like primary and secondary nitro compounds, primary and secondary nitroso compounds also exhibit
tautomerism with their more stable isonitroso or oxime form.
Ex.49 ,
CH CH CH
3 3
2-Nitrosopropane
|
NO
NOH
Acetoneoxime
|
CH C CH
3 3
|
Imine - Enamine system :
Imine
R CH CR = NR
2
Among these two tautomers, enamines are stable only when there is no hydrogen on the nitrogen, otherwise
the imine formpredominates.
Process of interconversion :
(a) Base-catalyzed enolization involves the intermediate of an enolate ion, and is thus a consequence
of the acidity of the o-hydrogen.
Protonation of the enolate anion by water on the o-carbon gives back the carbonyl compound.
Protonation on oxygen gives the enol. Notice that the enolate ion is the conjugate base of both the
carbonyl compound and the enol.
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CHEMISTRY
(b) Acid-catalyzed enolization
Involves the conjugate acid of the carbonyl compound. Recall that this ion has carbocation
characteristics. Loss of the proton from oxygen gives back the starting carbonyl compound ; loss of
the proton from the o-carbon gives the enol. Notice that an enol and its carbonyl isomer have the
same conjugate acid.
(c) Exchange of o-hydrogens from deuteriumas well as racemization at the o-carbon are catalyzed not
only by bases but also by acids due to the phenomenon of tautomerisation.
4.3 Carbocation
Definition : Acarbon intermediatewhichcontain threebondpair &a positivechargeonit is calledcarbocation.
Ex.50 , Methyl carbocation
CH
3
Ethyl carbocation
Hybridisation : Carbocation may be sp
2
& sp hybridised
Hybridisation Example
sp
2
sp H
2
C = , HC
Stability : Carbocation are stabilised by
(i) + I effect (ii) + m effect (iii) Hyperconjugation
Carbocations are electron deficient. They have only six electrons in their valence shell, and because of this,
carbocations are Lewis acids. In this way they are like BF
3
and AlCl
3
. Most of the carbocations are short-
lived and highly reactive, they occur as intermediates in some organic reactions. Carbocations react with
Lewis bases or ions that can donate the electron pair, that they need to achieve a stable octet of electrons
(i.e., the electronic configuration of a noble gas):
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CHEMISTRY
Because carbocations are electron seeking reagents, chemists call them electrophiles. Electrophiles are
reagents which in their reactions seek the extra electrons that will give them a stable valence shell of
electrons. All Lewis acids, including protons, are electrophiles. By accepting an electron pair, a proton
achieves the valence shell configuration of helium; carbocations achieve the valence shell configuration of
neon.
Ex.51 > >
t-Butyl carbocation has +I effect of three Me groups and also Hyperconjugation effect which makes it most stable.
Ex.52 > >
In Benzyl cation, Extensive Resonance is seen which stabilises .
In Ethyl carbocation + I and Hyperconjugation of Me group stabilizes carbocation, in vinyl carbocation
stability decreases rapidly since carbon of 'CH
2
' is sp
2
hybridized which is slightly more electronegative
hence acts as I atom which increases (+) charge.
Rearrangement : Whenever an Intermediate carbocation is formed in reaction it rearranges to a
more stable one.
Not all carbocations rearrange but only those which can produce more stable species can only rearrange.
Consider the following reactions.
(a)
This reaction involves formation of carbocation but no rearrangement.
(b)
(c)
Carbocation rearrangement can also occur by ring expansion.

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CHEMISTRY
One very stable carbocation reported is cyclopropylmethyl carbocation. This unique stabilisation is seen in
this case of three member ring only.
(more stable than Benzyl)
cyclopropyl methyl carbocation
4.4 Free radical
Ionic reactions are those in which covalent bonds break heterolytically and in which ions are involved as
reactants, intermediates, or products.
Another broad category of reaction mechanisms that involve homolysis of covalent bonds with the production
of intermediates possessing unpaired electrons called radicals (or free radicals):
Table : 1
Ex.53
H CC
3
CH
3
CH
3
>
3 2 3 3 3
H C H C C H CH H C C H
- - -
> >
(Stability order)
Ex.54
-
C ) H C (
3 5 6
>
H C ) H C (
2 5 6
-
>
2 5 6
H C H C
-
>
3
3 2
CH
|
CH C CH CH
-
= (Stability order)
4.5 Divalent Carbon intermediates : Carbenes
Definition : There is a group of intermediates in which carbon forms only two bonds. These neutral divalent
carbon compounds are called carbenes. Most carbenes are highly unstable compounds that are capable of
only fleeting existence. Soon after carbenes are formed, they usually react with another molecules. The
reactions of carbenes are especially interesting because, in many instances, the reactions showa remarkable
degree of stereospecificity.
Methods of preparation of carbene :
CHCl
3
+ : CCl
2
CH
2
I
2
+ Zn : CH
2
CH
2
N
2
N
2
| + : CH
2
CH
2
= C = O : CH
2
+ CO|
Types of carbene
Singlet Triplet
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CHEMISTRY
Table : 2
Shape Bent Linear
Hybridisation sp
2
sp
Nature of reaction stereospecific None
State Excited state Ground state
Magnetic Diamagnetic Paramagnetic
Nature Diamagnetic Diradical
4.6 Nitrenes
The nitrogen analog of carbenes are nitrenes. They are very reactive since in them octet of N is incomplete.
In nitrenes only one valencies of N are satisfied.
4.7 Benzyne
The benzene ring has one extra C C t bond in benzyne
Clearly, we can see that the newly formed t bond cannot enter in resonance with other t orbitals of ring.
since it is in perpendicular plane.
It is also important to note that hybridisation of each carbon involved in 'Benzynic bond' is sp
2
since the
overlap between these orbitals is not so much effective.
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CHEMISTRY
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1. Showby arrowI effect in the following molecules
(a) CH
3
CH = CH NO
2
(b)
Sol. (a) CH CH
3
NO
2
+o o
CH
+oo
(b)
O
-o
-o -o
-oo -oo
2. Arrange for acidic strength order CH
3
COOH, ClCH
2
COOH, Cl
2
CHCOOH, Cl
3
CCOOH
Sol. CH
3
COOH<ClCH
2
COOH< Cl
2
CHCOOH< Cl
3
CCOOH
3. Drawresonating structure for following molecules
, CH
2
= C = O ,
Sol.
+
+
+
CH = C = O
2
. ..
.
O
O C H C
2
,
N = N = N N N N
2

4. By drawing resonating structures of following molecules, Judge whether the group attatched to ring exerts
+ m or m effect.
,
Sol. (a)
O
||
CH C NH
3 (+M group)
NHCCH
3
O
NHCCH
3
O
(b)
CCH
3
O
CCH
3
O
(m effect group)
CCH
3
O
C
O CH
3
C
O CH
3
C
O CH
3
C
O
CH
3
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CHEMISTRY
5. Which of them is more basic :
(a) (b)
Sol. is more basic due to lone pair of N atom is not delocalized.
6. Which of them is more basic
(a) (b) (c)
Sol. is more basic due to sp
3
hybridized N atom.
7. In which of the following pairs the first one is the stronger base than second.
(A) , (B) ,
(C) , (D) CH
3
NH
2
, CH
3
OH
Ans. A, C, D
> >
8. Which of the following is least stable ?
(A) (B) (C) (D)
Ans. A
Sol. Is less stable due to bridgehead carbanion.
9. Write tautomer of butanone and cyclohexanone.
Ans. (a)
H O
|
CH CH C CH
3 3
= , (b)
10. Arrange the following carbocation s in stability order-
1. H
2.
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CHEMISTRY
Ans. (1) CH = CH CH
2 2
+
> >
(2)
+
>
+
>
+
Sol. (1) CH = CH CH
2 2
+
> >
(1 + resonance) (2 + hyperconjugation) (no resonance, no hyperconjugation)
(2) Stability order : 3 > 2 > 1
11. Which one of the following is most stable carbocation ?
(A)
2 2
H C CH CH

=
(B)
3
H C

(C)
H C CH CH
3

=
Sol. (A) is more stable due to resonance.
12. Arrange the following free radicals in increasing order of stability
Ans. V < III < I < II < IV
Sol. Resonance stabilized free radical is more stable.