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At the outset of the discussion on organic chemistry, we must make it clear that the fundamentals (involving
bond cleavage, various intermediates and their reactivities, types of reagents, field effects etc.) are the
backbone of entire organic chemistry. These concepts will be useful in understanding the organic chemistry as
a whole.

1. TYPES OF BOND CLEAVAGE


A covalent bond between two atoms can be broken in two ways:

(a) Homolytic cleavage: RX R X

In this type of cleavage, each atom separates with one electron leading to the formation of highly
reactive intermediates called free radicals. Homolytic cleavage occurs generally in the gas phase or in solution
in nonpolar solvents and is catalysed by ultra violet light or high temperature or by radical initiators like
peroxides, alkyl hypohalites, tetra ethyl lead (TEL) etc.

(b) Heterolytic cleavage: RX R X or R + X

In this type of fission, one atom may attract both the electrons leaving none for the other, resulting in a
negative and a positive ion (or ion pair). Heterolytic cleavage occurs in polar solvents because of the ease of
separation of charge and stabilization of the resultant ionpairs through solvation. In such heterolytic fission,
the charged species formed are either carbon bearing positive charge called carbocation or carbon bearing
negative charge called carbanion.

2. TYPES OF REAGENTS
There are basically two types of reagents used in organic chemistry, the electrophiles and
nucleophiles. Electrophiles are the electron deficient species while nucleophiles are the electron rich species.
Electrophiles are thus electron pair acceptors and nucleophiles are electron pair donors. In organic chemistry,
the interaction of electrophile i e. electron pair acceptors and nucleophiles i.e. electron pair donors is generally
observed. Electrophiles in other words are called Lewis acids & nucleophiles are called Lewis bases.

Electrophiles (Lewis acid)

Soft Acids
(Hg22+, Fe2+, Ag+, Cs+ etc.)
Metals of lower oxidation state.
They have low positive charge
density.

Hard Acids
(Fe3+, H, Li+, Na+, C etc.)
Metals of relatively higher oxidation
state. They have high positive
charge density.

Nucleophiles (Lewis bases)

Soft bases

( HSO 3 , HS, Cl, Br, I etc.)


Less electronegative elements
having low negative charge
density.

NH 2 ,

Hard bases

(
F, H, OH etc.) More
electronegative elements having
high negative charge density.

By (Hard and soft acid base) HSAB theory, soft acid binds with the soft base and hard acid prefers to
bind with hard base.
To be an electrophile, the species must have an element, which has suitable

vacant orbital. For example, CH 3 , BCl 3 , BF3 , AlCl 3 , H , Fe 2 , NO


2 , NO , Br , Cl , SO 3 , CO 2 etc. Similarly, the
nucleophiles
should have atleast one atom
with lone pair of electrons for donations.

NH
,
OCH
,
For example, F , Cl , Br , I , OH ,
2
3 CN , NC , H2 O, NH3 , RNH2 , R2 NH, ROH etc.

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Remember, NH 4 and H3O+ are neither an electrophile nor a nucleophile but NH 2NH3 is not an
electrophile but it is a nucleophile.
CH3COCH3, CO2, SO3 etc. can function as both electrophile as well as nucleophile depending upon the
condition.

3.

INDUCTIVE EFFECT

In a single covalent bond between unlike atoms, the electron pair forming bond is never shared
equally between the two atoms. It tends to be attracted a little more towards the more electronegative atom of
the
two.
First,
let
us
look
at
the
CC
bond
in
ethane.
This CC bond has no polarity because it connects two similar atoms. However, the CC bond in ethyl
chloride is polarized by the presence of an electronegative chlorine atom. This polarization is actually the sum
of three effects. In the first of these, the C 1 atom has been deprived of some of its electron density by the
higher electronegativity of Cl. Secondly, the electron deficiency of C 1 is partially compensated by drawing the
CC electrons closer to itself, resulting in polarization of this bond and a slight positive charge on the C 2 atom.
Thirdly, the polarization of the CC bond causes a (slight) polarization of three methyl CH bonds. The effect
of C1 on C2 is less than the effect of Cl on C 1 atom.
2+

1+

H3CCH2Cl
2

In ethyl chloride, Cl is said to have an electron withdrawing I effect. Thus, inductive effect is a

permanent effect operating in the ground state of the molecule, involving displacement of bonding
electrons towards atom of higher electronegativity. It will also operate in molecules containing double
bonds and triple bonds.
4+

3+

2+

1+

C4C3C2C1Cl

1 > 2 > 3 > 4


1 + 2 + 3 + 4 =

The Cl in this case exerts electron withdrawing inductive effect. The effect of Cl is most on C 1 and as
we go towards C 2, C3 and C4, the effect decreases. Thus, inductive effect is a distance dependent effect. It
decreases as we go away from the source and after the fourth carbon atom (C 4 ), the effect is so little that for
all practical purposes we assume that it cease to exist.
There are other type of groups, which exert electron releasing +I effect. Thus, the substituents or
functional groups can be classified as electronwithdrawing (I) or electrondonating (+I) groups relative to
hydrogen.
The order of decreasing inductive effects of most common groups is as follows,
+I groups: O > CO 2 > CR3 > CHR2 > CH2 R > D

I groups: NR 3 > NH 3 > OR 2 > NO2 > SO2R > CN > CO2H > F > Cl > Br > I > CHO >
COR > OH > NH2 > CCR > Ar > CH=CR2
For measurements of relative inductive effects, hydrogen is chosen as reference in the molecule
CR3H. If the H atom in this molecule is replaced by X (an atom or groups of atoms), and the electron density
in the CR3 part of the molecule is less than in CR 3H, then X is said to have a I effect. If the electron density
in the CR3 part is greater than in CR 3H, then X is said to have a +I effect. Deuterium is also electron donating
with respect to hydrogen. Amongst the sp3, sp2 and sp hybridized carbons, the order of I effect is sp > sp2 >
sp3.

4. ELECTROMERIC EFFECT
This is a temporary effect which involves complete transfer of a shared pair of
electrons towards one of the atoms linked by a multiple bond at the demand of attacking reagent. The atom
receiving the electron pair acquires a unit negative charge, while the other atom becomes positively charged.

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This effect takes place in only those molecules which contains multiple bonds and the effect of polarization
takes place only when the reagent approaches the substrate. The polarization will revert when the attacking
reagent is taken away from the substrate.
When
+ E effect.

the

electron

transfer

takes

place

towards

the

attacking

reagent,

it

is

called

CH3 H

H
CH3
H
CH3
C=C
+ H+

C
H
H
H
H

HCCH

H
Isopropyl carbonium ion
(+ E effect)

And when
called E effect.

the

electron

transfer

takes

place

C = O + CN

away

CO

from

the

attacking

reagent,

it

is

(E effect)

CN
The most common example of the electromeric effect is the reaction of an alkene with bromine in CCl 4.

R
C

Br2 in
CCl4

Br

R
C

Br

Br

Br

Br

R Br
C

C
Br

Cyclic bromonium ion

Vicinal dibromide

In this reaction, when reagent (bromine) approaches alkene, the temporary polarization develops on
the alkene with C2 atom gaining a negative charge and C 1 atom acquiring positive charge (as it can be
compensated by the +I effect of R group). The alkenes being electron rich compounds (due to the presence of
electron cloud) are attacked by the electrophile (Br+) to give a cyclic bromonium ion. Here, the formation of
cyclic bromonium ion as intermediate is possible because bromine has large size and possess the lone pair,
which can be donated to the carbon (C 1) simultaneously. The cyclic bromonium ion is then attacked by Br
from the opposite side of the 3membered cyclic intermediate to give the resultant vicinal dibromide product.

5. RESONANCE EFFECT
Formation
of
a
centre
of
high
and
low
electron
density
by
the
transfer
of
electrons
from
one
part
of
conjugated
(alternate
single
and
double
bonds)
system to the other is called Resonance effect or Mesomeric effect. This is a permanent effect, which
occurs in the ground state of the molecule. Groups, which withdraw electrons from the conjugated system are
said to possess R or M effect. (e.g. NO2, CN, >C=O). The groups, which donate electrons to the
conjugated
system
are
said
to
possess
+
R
or
+
M
effect.
(e.g.
X,
NH2 , OH, OCH3).
Conditions needed for a compound to show resonance are
(a) The molecule must have conjugation. For example,

..

CH2=CHCH=CH2, CH2=CHCH2, CH2=CHCH2, CH2=CHCH2,


..

CH2=CHOH,
CH2=CHN
..

O
etc.
O

(b) Part of the molecule having conjugation should be exactly or nearly planar. The orbitals participating
in resonance must be of almost equal sizes and should also be smaller in size. Bigger orbital donot
..

..

overlap effectively. For example, CH2=CHOH


will show greater resonance than CH2=CHCl
..
.. : as

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the size of O and C (both belong to same period) matches more than the size of C and Cl (C
belongs to second period while Cl belongs to third period).
The resonance shown by benzaldehyde is depicted as:

H
C

H
C

( R effect)

The resonance shown by chlorobenzene is represented as:

Cl

Cl

Cl

Cl

Cl

(+ R effect)

The various structures drawn for a molecule are called canonical or resonating structures.

RULES FOR DRAWING RESONATING STRUCTURES


As we have seen the one way of expressing the actual structure of a molecule containing delocalized
bonds is to draw several possible structures and to assume that the actual molecule is a hybrid of them. These
canonical
forms
have
no
existence
except
in
our
imaginations.
The molecule does not rapidly shift between them. It is not the case that some molecules have one canonical
form and some another. All the molecules of the substance have the same structure. The structure is always
the same all the time and is a weighted average of all the canonical forms. In drawing canonical forms and
deriving the true structures from them, we are guided by some simple rules, which are as follows:
1. All the canonical forms must be bonafide Lewis structures. For instance, none of them may have a
carbon with five bonds.
2. The positions of the nuclei (atoms) must be same in all the structures. This means that when we draw
various canonical forms, we cannot change the relative position of atoms but can change the relative
position of electron pairs (bonding and nonbonding).

Cl

Cl

Cl

Cl

Cl

Cl

The resonance interaction of chlorine with the benzene ring can be represented as above. In all the
structures
involving
resonance,
the
sigma
bonds
are
not
participating,
only
the or unshared electrons are put in different ways. This means that if we write
one canonical form for a molecule, we can write the others by merely moving and/or unshared
electrons.
3. All atoms taking part in resonance i.e. covered by delocalized electrons, must lie in a plane or nearly
so. This of course does not apply to atoms, which have the same bonding in all the canonical forms.
The reason for planarity is maximum overlap of the porbitals.

4. All canonical forms must have the same number of unpaired electrons. Thus CH2CH=CHCH2 is a
.
.
valid canonical form but CH2CH=CHCH2 is not a valid canonical form for 1,3butadiene.
5. The energy of the actual molecule is lower than that of any canonical form or contributing form
obviously. Therefore, delocalization is a stabilizing phenomenon.

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6. All canonical forms do not contribute equally to the true molecule. Each form contributes in proportion

to its stability, the most stable form contributing most. Thus, for ethylene, the form CH2CH2 has such a
high energy compared to CH2=CH2 that it essentially does not contribute at all. Equivalent canonical
forms contribute equally. The greater the number of significant structures that can be written and the
more nearly equal they are, greater will be the resonance energy provided other things are equal.

It is not always easy to decide relative stabilities of imaginary structures; the chemists are often guided
by intuition. However the following rules may be helpful.
(a) Structures with more covalent bonds are generally more stable than those with fewer covalent bonds.

For example, CH2=CHCH=CH2 is more sable than CH2CH2=CHCH2.


(b) Stability is decreased by an increase in charge separation. Structures with formal charges are less
stable than uncharged structures. Structures with more than two formal charges usually contribute very
little. An especially unfavorable type of structure is one with two like charges on adjacent atoms.
(c) Structures that carry a negative charge on a more electronegative atom are more stable than those in
which the charge is on a less electronegative atom. Also it is favorable to have positive charge, carried
..

O:
O:
..
by low electronegative atom. For example, CH2CH=N
is less stable than CH2CH=N .. .
O
O
(d) Structures with octet of every atom being complete are more stable than any other structure. For
..

..
example, RCHOH
.. is less stable than RCH=OH.

..
Draw resonating structure of RC+=O: and compare the stabilities of contributing
structures.

6.

HYPERCONJUGATION

This effect takes place only when a saturated carbon with a Hatom is linked to
an unsaturated carbon. This involves the conjugation between electrons of a single carbonhydrogen bond
and the electron of the adjacent multiple bond. It is also called no bond resonance because in the different
canonical
forms,
no
bond
is
shown
between
carbon
and H atom of the alkyl group. For example, resonance structures of ethyl cation can be
shown as follows.
H H
H H
H H
H H

HC C HC = C H C = C HC = C
H H

H H

Hyperconjugation is also possible in alkenes and alkyl arenes. For example, for propene, it can be
shown as follows,

H
HC
H

CH=CH2

HC=CHCH2
H

H
H C=CHCH2
H

H
HC=CHCH2
H

As we have seen, the inductive effect of alkyl groups is in the order R 3C > R2CH > RCH2 > CH3.
However, in some reactions, the electron releasing order of alkyl groups reversed. For example, the rate of
reaction of psubstituted benzyl bromide with pyridine in acetone (follows S N2 pathway) is just opposite than
that expected from the electron release by the inductive effect. That is, the methyl substituted compound
reacted fast and the isopropyl substituted compound reacted slower and the tbutyl substituted compound
reacted slowest. The rate order for the R groups was Me > CH3 CH2 > isoPr > tBu.

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CH2

Br

:N

CH2 N

Br
Thus, the order of electron release is exactly the reverse of inductive effect of alkyl groups. Therefore,
alkyl groups must also possess some other mechanism of electron release in which the order is Me >
CH3CH2 > isoPr > tBu. This effect is called as Hyperconjugation effect or BakerNathan effect (after its
discoverer).
This
effect
is
stronger
than
inductive
but
weaker
than resonance effect generally. The hyper conjugation effect in toluene (methyl benzene) can be shown as:
H
H
H
H
H

H C H
..

C H

C H
..

..
This help us in predicting the o/pdirecting influence of CH3 towards electrophilic substitution.

In addition to the participation of hydrogen atom in hyperconjugation as shown above, chlorine atom
can also takes part in hyperconjugation as observed in trichloro methyl benzene. The hyperconjugation in alkyl
groups is classified as +H while in trichloro methyl is classified as H effect.
Cl
Cl
Cl
Cl
Cl
Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

This explains the mdirecting nature of CCl3 group.

Illustration 1
Question:

Explain the observed heat of hydrogenation of the following olefins.


Olefin

Solution:

(Heats of hydrogenation in kcal/mole)

CH2=CH2

31.0

RCH=CH2

28.5

RCH=CHR
(cis)

27.0

RCH=CHR
(trans)

25.7

The stability order of these alkenes according to the hyperconjugation theory would be
RCH=CHR > RCH=CHR > RCH=CH2 > CH2=CH2
(trans)
(cis)

7. VARIOUS INTERMEDIATES
Whenever a reaction takes place in organic chemistry, the reactants are not directly transformed into
the products. The reaction proceeds via some intermediates, which are formed during the course of reaction
and are not very stable species. The most common transient intermediates formed are radicals, carbocations
and carbanions but other reactive intermediates possible are carbenes, nitrenes and benzynes. The formation
of these intermediates and their characteristic reactions have been dealt here in brief.
Note that transition state is also formed during the conversion of reactant to products but they are
different than intermediates. Transition states are less stable (short livedhigh energy content) species than
the intermediates, so transition states are not isolable but intermediates are isolable. Transition states have

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bond in the formation as well as breaking stage while in intermediates bond breaking and/or bond making
process has taken place completely.

7.1 FREE RADICALS


Their formation is initiated mostly by ultraviolet light. For example,

ClCl 2Cl

RH + C l R + HCl

R + ClCl RCl + C l etc.


This alkyl group bearing an odd unpaired electron is called alkyl radical. The radicals are deficient in
one electron to complete its octet and are paramagnetic in nature. A free radical has a carbon in the sp 2
hybridised state, thus exhibit planar (flat) structure. If a free radical with three different atoms or group of
atoms is attacked by another radical, it leads to the generation of a stereocentre, existing as enantiomeric pair.

R
C
R

Cl

Cl + Cl
R

Enantiomeric pair

The free radicals can be attacked either by another free radical or by a neutral molecule whose bond
(whether or ) will be broken homolytically. Free radicals have very less or no tendency to rearrange to give
a more stable radical.

R
C

R
C

Carbocation T.S.

Radical T.S.

Carbanion T.S.

Whenever a intermediate rearranges, it goes through a transition state. The transition states for the
rearrangement of carbocation, radical and carbanion are shown above.
These transition states involve two, three and four electrons, respectively and electrons in excess of
two can be accommodated only in an antibonding molecular orbital of much higher energy. However 1,2aryl
and halogen shifts are known in radicals, which involve stabilized, bridged transition state. The driving force for
the rearrangement is to attain stability.
We are aware that the stability order of free radicals is 3 > 2 > 1 alkyl, if electron releasing groups
are attached. For example,

Me3CO

Ph2MeCCH2C=O

Ph2MeCCH2C=O

CO

Ph2MeCCH2
1 radical

PhMeCCH2Ph + RC=O

RCHO

Ph

PhMeCCH2

PhMeC

CH2

3 radical

The rearranged radical is more stable than the original one not only because the former is primary and
the latter is tertiary but also because it is stabilized by delocalization of the unpaired electron over the orbital
system of benzene nucleus. It is significant that only Ph migrates, despite the fact that migration of Me would
yield

even

more

stabilized

radical,

Ph 2 C CH 2 Me.

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This probably reflects the energetic advantage of the migration of Ph via a bridged delocalized transition state.
When no Ph group is present, as in EtMe2CCH2CHO, no migration takes place at all and the end product is
EtMe2CCH3.

7.2 CARBOCATIONS
Carbocation is the carbon containing intermediate bearing a positive charge and having a sextet of
electrons in its outermost shell. The carbocation can act as a electrophile. Let us first see the carbocation
formation from different substrates.

..

..

ROH
.. 2 R + H2O

CH2=CHCH2OH
..

ROH
..

CH2=CHCH2OH2

H2O

CH2=CHCH2
Carbocation

CH2CH=CH2
RCl

Polar

R + Cl

Solvent

+ E

H
E

H
E

The most characteristic feature of carbocations is that they undergo rearrangements readily (if
possible). The driving force for the rearrangement is to attain stability. The driving force for the rearrangement
is
to
attain stability. The stability order of carbocations is 3 > 2 > 1 alkyl,
if electron donating groups are attached. The rearrangement may or may not involve change in carbon
skeleton.
Now, let us consider the case in which carbocation undergoes rearrangement without change in carbon
skeleton. For example, 1propyl cation rearranges to 2propyl cation by the migration of a hydrogen atom with
its
electron
pair
(i.e.
as
H)
from
C2
to
the
carbocationic
C1
by
1, 2hydride shift.

CH3CHCH2

1, 2hydride

1 carbocation

CH3CHCH3

shift

2 carbocation

This reflects the greater stability of a secondary carbocation rather than a primary carbocation.
However,
shift
in
the
reverse
direction
can
also
take
place
where
this
makes
available the greater delocalization possibilities of the orbital system of a benzene ring.
(i.e. Tertiary Secondary). For example,

(3 Carbocation)

CH3
CH3C
OH

CH3
CCH3

~CH3

PhCHCMe2

PhCHCHMe2
(2 Carbocation)

CH3C

CH3
CCH3

:OH
.. CH3

CH3
CH3C

CCH3

OH
CH3
..

The migrating aptitude of various groups is


(a) H > 3 > 2 > 1 alkyl > CH 3
(b) Ph > CH 3
(c) panisyl > ptolyl > phenyl > pchlorophenyl > pnitro phenyl.

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Carbocation has a trigonal planar structure, as the carbon atom of carbocation is also sp 2 hybridised. A
carbocation can act as an electrophilic reagent and it leads to the formation of racemic mixture if the three
groups attached to the carbocationic carbon are different and incoming nucleophile is different than the 3
groups already present.

R
C

Nu

Nu + Nu
R

Racemic mixture

7.3 CARBANIONS
Carbanions are anions of carbon, generated by the removal of one of the groups attached to a carbon
atom without removing the bonding electrons. For example, nitromethane reacts with alkali to yield an anion,
which is stabilized by resonance.

H
CH2NO2

H
CH2C

B
BH

CH2 N

O
H

B
BH

CH2

+ BH

O
..
CH2 C
H

CH2=C

Enolate ion

In general, compounds containing methylene groups flanked by nitro, cyano or carbonyl groups show
acidic character as the hydrogens can be removed as protons leaving a resonance stabilized anion. Alkyl
carbanions can only be formed under extreme conditions, since the attached groups are not capable of
dispersing the negative charge.
Carbanion assumes a pyramidal configuration, as carbon atom here is sp3 hybridised.
The unshared electron pair would be accommodated in an sp 3 hybridised orbital. The unshared electron pair
would be accommodated in an sp3 orbital. The carbanions readily undergo pyramidal inversion also called
umbrella inversion.
R
..
R

R
C

C
R

..

Carbanions are capable of acting as nucleophiles and will attack the substrate on a site of lower
electron density.

HCCH2CH

B
BH

..
HCCH

O
CH

HCCH=CH

HC=CHCH

Illustration 2
Question:

Arrange the following carbanions in the order of their stability.


..
CH2

..
CH2

..
CH2

..
CH2

NO2
NO2
(I)

(II)

OMe
OMe
(III)

(IV)

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Solution:

NO2 group shows I and R effect from para position, thus stabilizing the carbanion by dispersal of ve
charge through resonance (mostly) while NO2 from meta position would be able to exhibit only I effect,
so carbanion ( II) is stabilized only by I effect of NO2. OMe group shows I and +R effect but since +R
effect is more prominent than I effect, the carbanion ( III) is destabilized while OMe from meta position
exerts only I effect would stabilise the carbanion ( IV). I effect of NO2 group is stronger than the I effect
of OMe, thus the order of stability of these carbanions are
(I) > (II) > ( IV) > ( III)

7.4 CARBENE
A reaction in which both the groups or atoms are lost from the same carbon is called elimination
reaction and results in the formation of carbenes.
Carbenes can be defined as neutral, divalent carbon intermediates in which a carbon is covalently
bonded to two atoms and has two nonbonded orbitals containing two electrons between them. There are two
kinds of carbenes, singlet and triplet. In the singlet state, a carbon atom is presumed to be sp2 hybridized. Two
of the three sp2 hybrid orbitals are utilized in forming two covalent bonds whereas the third hybrid orbital
contains the unshared pair of electrons. The remaining porbital remains vacant. Thus, singlet carbene
resembles a carbonium ion very closely. On the other hand, carbon atom of a triplet carbene is sp hybridized
and it is a linear species. These two hybrid orbitals are involved in the bond formation with two groups and the
remaining two electrons are placed, one each, in the equivalent, mutually perpendicular p y and pz orbitals.
These electrons have parallel spins and a carbene with this structure is said to be in a triplet state.

R
C

C
R

(triplet carbene)

(singlet carbene)

At first sight, it appears that a singlet carbene has lower energy as the unshared electron pair is in a
sp hybrid orbital but the consideration of the electron repulsion energy that must be overcome to pair two
electrons in a single orbital places it at a higher energy level than a triplet structure. Thus, the triplet state of a
carbene is more stable than the singlet state. Triplet carbenes are not linear but have a bond angle of 140 to
150.
2

Among diholocarbenes, the order of stability is


..
..
..
..
Singlet carbenes: CF2 > CCl2 > CBr2 > CI2
..
..
..
..
Triplet carbenes: CF2 < CCl2 < CBr2 < CI2
Generation of carbene
(a) From Diazoalkanes and Ketenes

CH2NN

CH2=C=O

h/
N2

CH2

CH2

Singlet

Triplet

h
CO

CH2

CH2

(b) From carbanions

O
Cl3CC

CO2

Cl3C

Cl

CCl2

(c) From chloroform

Cl
HCCl
Cl

B
BH

Cl
:CCl

..
Cl + CCl2

Cl

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Reactions of carbene
(a) Cycloaddition reactions
(b) Insertion reactions
Singlet carbenes add to alkenes in a stereospecific fashion, i.e. the stereochemistry of the alkene is
retained in the cyclopropane.

In contrast, the addition of triplet carbenes to alkenes takes place nonstereospecifically.


The stereochemistry of these cycloadditions is so specific that it may be used as a diagnostic test for
the identification of singlet and triplet carbenes. The difference in the behaviour between these two electronic
states of a carbene to an alkene is a concerted process as there is no spin restriction on the simultaneous
formation of two new bonds of the cyclopropane and hence it is a stereospecific process. In contrast, the
cycloaddition of a triplet carbene is a stepwise process. The first step leads to a triplet diradical, which
undergoes spin inversion, before it forms cyclopropane. Since this diradical has a CC single bond, there is a
possibility of free rotation about that bond. If this rotation is faster than spin inversion, the reaction becomes
nonstereospecific.

+ CH2

C=C

C
CH2

Frequently, carbenes can be inserted into a CH bond, to increase the length of carbon chain.

X
C

H + :CX 2 C

CH
X

Alkylated and phenylated carbenes can also undergo ready rearrangement, to directly give final
product (alkene).

R
RCH

..

~R

CH

RCH

CHR

RCH=CHR

Carbene are capable of acting as electrophiles. It is involved in ReimerTiemann reaction and


Carbylamine reaction.

7.5 NITRENE
Such intermediates result from the elimination of a proton and a leaving group (generally halogen) from
the nitrogen of a substrate. For example,

..
RCNBr
..
O

B
RCNBr
..
BH
O

..

..

R N =N = N
..
RN=C=O

or h

or h

..
Br + RCN: (acyl nitrene)
O

..

RN: + N2

..
RN: + CO

Nitrenes are also electrically neutral nitrogen containing species with four unshared electron pairs and
one bond pair of electrons. Here, nitrogen is the electron deficient atom.
The reactions of nitrenes are similar to those of carbenes. Thus, nitrenes also undergo addition to C=C
bonds and insertion into CH bonds. For example,

..

R N + R2C=CR2

N
R2C

CR2

Page 12

..
CH + N:

..
CNHR

R
Alkylated nitrenes can also undergo rearrangement to give final product (neutral).

..
RCN:

..
RNC=O

~R

RN=C=O
Alkyl isocyanate

7.6

BENZYNE

These intermediates are generated by the elimination of proton and a leaving group (generally
halogen) from the adjacent carbons from a benzene ring system. For example,

Cl
H
NH2

Cl

NH2
NH3

Cl

..
Benzyne
..
NN

NaNO2 / HCl

CO2H

05C

decomposes

NN + O=C=O +

CO
O

Br
Cl

MgBr

Mg (1 equiv.)

MgBrCl +

THF

Cl

Benzynes are very reactive. Neither benzyne nor any other aryne (substituted benzyne) has yet been
isolated under ordinary conditions. The triple bond in benzynes is not identical with the formal triple bond of
alkynes because here the two bonds are formed by the overlapping of P zPz and sp2sp2 orbitals whereas
in alkynes, they are formed by the overlap of P zPz and PyPy orbitals.
It should be noted that the bond (resulted from sp2sp2 overlap) is a very weak bond, which can be
easily ruptured by the attack of a nucleophile (they cannot be attacked by electrophiles), thus making
benzynes very reactive. Another feature to be noted is that the extra pair of electrons does not affect the
aromaticity of benzene nucleus. The original sextet still functions as a closed ring and the two additional
electrons are merely located in a orbital that covers only two carbons. In a reaction where benzyne is
formed, if the solution does not have sufficient nucleophile, they undergo dimerization to give biphenylene.
Dimerization

Biphenylene

8.

APPLICATION OF INDUCTIVE AND RESONANCE EFFECTS

To explain the stability of carbocations, free radicals and carbanions and the acidic and basic strengths
of various organic compounds, the above effects work very well.

8.1 STABILITY OF CARBOCATIONS, FREE RADICALS AND CARBANIONS


Let us first compare the stabilities of following carbocations,

H
HC

H
RC

RC

RC

Methyl
Carbocation

1 carbocation

2 carbocation

3 carbocation

Page 13

Alkyl groups are electron donating, therefore more the number of alkyl groups, more will be the stability
of the carbocation. Thus, stability of given carbocation follows the order 3 > 2 > 1 > CH 3. If we consider the
resonance effect shown by allyl, benzyl groups, then more stability is observed for the adjacent carbon bearing
positive charge. The order of stability for different carbocations is shown as:
(CH3)3 C+ > PhCH2 + > CH2=CHCH2 + > (CH3)2 CH+ > CH3CH2+ > CH3 + > CH2=CH+.
The observed anomaly for 3 cation with benzyl carbocation can only be explained if we consider the
combined effect of hyperconjugation and inductive effect, which outweighs the sole resonance phenomenon
shown by benzyl carbocation.

In general, electron releasing groups increases the stability of carbocation and electron withdrawing
groups decreases their stability.
Now let us compare the stabilities of free radicals.

H C

R C

R C

Methyl
free radical

1 free
radical

R
R C

2 free
radical

3 free
radical

As
free
radicals
are
electron
deficient
and
R
groups
are
electron
donating,
more the R groups more will be the stability of free radicals. Thus, stability order of free radicals is 3 > 2 > 1
> CH3.
The effect of electron releasing and electron withdrawing groups on free radicals is same as that of
carbocations.
Finally, let us compare the stabilities of carbanions.
H

H C:

R C:

R C:

Methyl
carbanion

1 carbanion

2 carbanion

R
R C:
R
3 carbanion

The stability of the carbanion decreases due to the presence of alkyl groups, as the negative charge on
the
carbon
would
be
intensified.
Thus,
the
order
of
stability
of
carbanion
is
CH3 > 1 > 2 > 3.

In general, electron releasing groups destabilize the carbanions while electron withdrawing groups
stabilizes them.
8.2 ACIDIC STRENGTH OF ORGANIC ACIDS
The factors responsible for influencing the acidity of an organic compound, HX are
(a) the strength of the HX bond
(b) the electronegativity of X
(c) factors stabilizing X as compared to HX and
(d) the nature of the solvent.
The most important factors among all is (c). More stable (less basic) the conjugate base is, more acidic
the compound will be. On comparing the acidic strength of two compounds, the compound having greater
acidity will have higher value of Ka and lower pK a value.
Now let us see using any of these factors, how we can predict the order of acidic strength for organic
acids.
(i) Alcohols: If we were to predict the order of acidic strength of ethanol, isopropanol and tertiary
butanol, we can proceed as

Page 14

Me

Me CH2 O H

Me

CHOH
Me

Me

C OH
Me

As alkyl groups (methyl group) have a +I effect, the electron density at the oxygen atom will increase.
More the number of alkyl groups, more will be the intensity of negative charge on oxygen. The greater the
negative charge on the oxygen atom, the closer is the electron pair in the OH bond driven to the hydrogen
atom and consequently separation of a proton becomes increasingly difficult. Thus, the acidic strength of given
alcohols will be in the order
Ethanol > isopropanol > tbutanol

In general, electron releasing groups decreases the acidity while electron withdrawing group increases
the acidity of a compound.
Of the ethanol and trifluoro ethanol which is more acidic?
(ii) Phenols and substituted phenols:
(a) Because of resonance, the oxygen atom of the OH group acquires a positive charge and so proton
release is facilitated.

..

:O H

:OH

:O H

:O H

..

..

..

:O H

..
It might be noted that since the carbon atom of COH group is sp2 hybridised, it is more
electronattracting than an sp3 carbon atom (as in alcohols) and therefore there is an increased
I effect which facilitates proton release. But this inductive effect alone is not large enough to explain the
increased acid strength of phenols as compared with alcohols.
(b) When phenol ionizes, the phenoxide ion is also a resonance hybrid, but it is more stabilised by
resonance than is the unionized phenol molecule because of spreading of negative charge only. In the
unionized molecule, unlike charges are spread and so is less stable.

OH
+ H2O

H3O+ +

..
..

Phenols are stronger acids than alcohols. This is attributed to the fact that in phenoxide anion (obtained
by the loss of proton from phenol), there is possibility of the delocalization of its negative charge through
interaction with the orbitals of the aromatic nucleus while alkoxide cannot be stabilized by such effect. Thus
phenoxide is a weaker base than alkoxide. Consequently, the phenol would be stronger acid than alcohol.
The effect of a ring substituent on the acid strength of phenol depends on whether the group is electron
attracting or releasing, its ability to enter into resonance with the hydroxyl group, and its position. Effects in the
oposition are similar to those in the pposition, but there are added complications due to the steric effect and
to hydrogen bonding (when this is possible). Effects from meta position are altogether different from ortho and
para position. In general, the presence of electron withdrawing groups in phenol increases its acidity while the
presence of electron releasing groups decreases the acidity of phenol.
The methyl group decreases the acid strength of phenol from all ring positions. The methyl group is
electron releasing and so release of a lone pair from oxygen (of the OH group in the unionized phenol or from
the O in the phenoxide ion) into the ring is opposed. This results in diminished resonance in the contributing
structures and consequently the phenoxide ion is more resonance stabilised with respect to phenol than is the

Page 15

methylphenoxide ion with respect to methylphenol. Hence, phenol is a stronger acid than all methylphenols.
The order of acidity of methyl phenols is phenol > mmethyl phenol > pmethylphenol > omethyl phenol.
Now, let us compare the acidic strength of o, m and p nitrophenols. The corresponding phenoxide
ions obtained from the three nitrophenols would be stabilized by delocalization as
..
:O:

O
NO2

O
NO2

..

..

..

onitrophenoxide

O
N

..
:O:

O
..
:O:

NO2

..
:O:

..

NO2

..

NO2

NO2

mnitrophenoxide

..
:O:

..
:O:
:

..
pnitrophenoxide

NO2

..

NO2

NO2

N
O

NO2

N
O

N
O

From the structures of phenoxide ions, it is evident that o and pnitrophenoxides are more extensively
stabilized with respect to mnitro phenoxide (as additional contributing structure is obtained by the dispersal of
negative charge over oxygen atom of NO 2 group also in o and pnitrophenoxide but not in
mnitrophenoxide). Thus, corresponding o and pnitrophenols are much stronger acids than mnitrophenol.
A metanitro group cannot enter into resonance with the hydroxyl group but can exert I effect for this
position. Hence, metanitrophenol is also stronger acid then phenol. Out of o and pnitrophenols,
pnitrophenol is slightly stronger than oisomer as oisomer involves intramolecular hydrogen bonding, thus
having a reduced tendency to release proton.
O
O
H
N
O

The order of acidic strength of the nitrophenols is


pnitrophenol > onitrophenol > mnitrophenol > phenol
The cumulative effect of three nitro groups in the 2,4,6 positions is shown by the fact that 2,4,6
trinitrophenols (picric acid) is a very strong acid.
All the halophenols are stronger acids than phenol and so it follows that the I effect of halogen atom is
greater than its +R effect. Thus, the order of acidity of halophenols is ohalophenol > mhalophenol >
phalophenol > phenol.

Page 16

OH

OH

Me

Me

Which phenol is more acidic,

or
Me
NO2

NO2

Me

Among methoxy phenols, the order of acidity is:


mmethoxyphenol > phenol > omethoxy phenol > pmethoxy phenol.
(iii) Aliphatic carboxylic acids:
The aliphatic carboxylic acids are much stronger acids than phenols and alcohols. This is attributed to
the fact that the carboxylate ion (obtained by the loss of proton from carboxylic acid) is relatively more
stabilized by delocalization than the phenoxide and alkoxide ions with respect to their undissociated
molecules.

RCOH
O

RCO + H+
O

The delocalization of the negative charge in the carboxylate anion involves structures of identical
energy content (as the negative charge resides on more electronegative atom, oxygen) while in phenoxide
anion, the negative charge also resides on the less electronegative atom (carbon) making these structures of
high energy content with respect to those structures in which the negative charge is on oxygen. The presence
of electronwithdrawing substituents in simple aliphatic acids increases their acidity while the
electronreleasing substituents have reverse effect. For instance, let us compare the acidic strength of
fluoroacetic acid and acetic acid.

CH3COH

CO + H+

CH3

O
FCH2COH

CH2

O + H+

The fluoro acetate ion is stabilized more due to strong I effect of fluorine, with respect to acetate ion.
Hence, fluro acetate ion is less basic than acetate ion, thereby making fluoroacetic acid stronger than ac etic
acid. If there is a doubly bonded carbon atom adjacent to the carboxyl group, the acid strength is increased.
This will be evident if we compare the acid strength of propanoic acid and propenoic (acrylic) acid.

CH2=CHCO2H

CH2=CHC

+ H+

O
CH3CH2CO2H

CH3CH2C

+ H+

As we know that unsaturated carbon atom in propenoate ion is sp2 hybridised, which means that
electrons are drawn closer to the carbon nucleus than in a saturated, sp 3 hybridised carbon atom, due to
greater scontribution in the sp2 hybrid orbital. The result is that sp2 hybridised carbon atoms are less
electrondonating than saturated hybridised ones, thus, propanoate ion will be comparatively less stabilized
than propenoate ion, thereby making propenoic acid stronger than propanoic acid (but propanoic will still be
weaker than methanoic acid).If there is a triple bonded carbon atom adjacent to carboxyl group, the acid
strength is more with respect to the presence of a doubly bonded carbon atom adjacent to CO2H group. This
is attributed to the fact that sp hybridized carbon atoms are less electronreleasing than sp2 hybridized carbon
atoms.
Some other trends of acidity are:
HCO2H > CH3CO2H > CH3CH2 CO2 H > ..
HO2CCO2H > HO2CCH2CO2 H > HO2 CCH2CH2CO2 H > ..
These trends reflect that in any homologous series, when we move from lower members to higher
members, the acidity decreases.

Page 17

(iv) Aromatic carboxylic acids

It has been pointed out that replacement of the hydrogen atom in formic acid by an alkyl group
weakens the strength of the acid and the greater the +I effect of the R group, the weaker is the acid.
Phenylacetic acid, PhCH2CO2 H is stronger than acetic acid and therefore the phenyl group has an overall I
effect. On the other hand, benzoic acid is weaker than formic acid. In this case, the phenyl group has a overall
releasing effect (which is smaller than that of methyl group). These apparently contradictory results may be
explained as follows. When the carboxyl group is directly attached to the nucleus, the resonance effect (+R)
overcomes the I effect (in phenylacetic acid the phenyl group is insulated from the carboxyl group by a CH2
group and so the +R effect is not possible):
O

C
OH

C
OH

OH

+R

+R

This prevents to a large extent, the lone pair on the O atom of the OH group from entering into
resonance with the CO group. The result is a smaller positive charge on the O atom of the
OH group and so proton release is more difficult than in formic acid. The fact that benzoic acid is stronger than
acetic acid means that [I+(+R)] < [+ I+(+H)] of the methyl group.
The same arguments may be applied to ionised benzoic acid.

O
+

C + H2O

H3O +

OH

C
O

+R

Now let us consider substituted benzoic acids. At this point, we will consider the effect of substituents
from
m
and
ppositions
only.
First
let
us
take
methyl
substituted
benzoic
acids.
As the methyl group has + I effect, so the net result will be to increase the +R effect in the m or ptolyl group.
Since,
the
inductive
effect
decreases
with
distance,
so
the
+I effect of CH3 from para position would be less than the + I effect of CH3 group from meta position. Thus, the
electrondensity in the OH bond of mmethyl benzoic acid would be greater than that in pmethyl benzoic
acid. Accordingly, the pisomer should be more acidic than the misomer. But in real practice, the order is
reverse. Actually, we have ignored the hyperconjugation effect of CH3 group. Due to hyperconjugation effect of
CH3 in pisomer, the electron density in the OH bond would be increased greatly with respect to that in
misomer.

OH

CH

H+
CH

OH

OH
C

OH
C

OH
C

..

H+
CH
H

OH
C
..
etc.

..
HCH

HC H+

etc.

HC H+

H
H
H
Thus, the release of proton is fascilitated easily in misomer than in pisomer.

Page 18

Secondly, let us take nitro substituted benzoic acids. As the NO2 group exerts I and R effect (both
reinforcing each other), the electrondensity from the OH bond would be withdrawn, thus destabilizing the
OH bond and making m and p nitro benzoic acids stronger than benzoic acid.
O
O H
O
O H
C
C

NO2
N+

O O
As it is clear that NO2 group exerts its electron withdrawing resonance effect from the pposition and
not from mposition, thus withdrawal of electron density from the OH bond is greater in pnitro benzoic acid
than mnitro benzoic acid. Thus, pisomer is stronger acid than mnitro benzoic acid.
Thirdly, we compare the acid strength of m and p methoxy benzoic acid. OMe group exerts I and
+R
effects.
The
electronreleasing
resonance
effect
(+R)
is
operative
in pmethoxy benzoic acid and not in mmethoxy benzoic acid while I effect is operative in both the isomers.
Thus, the electron density is greatly increased in the OH bond in pisomer than in misomer, thereby making
misomer stronger acid than pisomer.

OMe
O

O
C
..

etc.

..
:OMe
..

OMe
..

OMe
..

The orthoeffect. This is a steric effect that is shown by osubstituents. Nearly all osubstituted
benzoic acids are stronger than benzoic acid due to this ortho effect irrespective of the polar nature of the
osubstituent.
As we have seen that benzoic acid is a resonance hybrid and so the carboxyl group is coplanar with
the ring. An osubstituent tends to prevent this coplanarity. Thus, resonance is diminished (or prevented) and
so the O atom of the OH group has a greater positive charge, resulting in increased acid strength. It follows
from this that greater the steric inhibition of resonance, the stronger is the acid. Support for this is the follow ing
order of strengths of substituted benzoic acids.
2, 6diMe > 2tBu > 2Me
Here again, if we consider the stability of the anion, steric inhibition of resonance prevents the +R effect
of the ring coming into operation and since this weakens acid strength, its absence results in increased acid
strength.
oHydroxybenzoic acid (salicylic acid) is far stronger than the corresponding m and pisomers. Steric
inhibition of resonance cannot explain this very large increase, since the corresponding methoxybenzoic acids
all have almost similar strengths. The carboxylate ions of ohydroxybenzoic acid is stabilised by intramolecular
hydrogen bonding while such hydrogen bonding is not feasible in omethoxy benzoic acid and support for this
is given by the following order of acid strength,
2, 6diOH > 2OH > benzoic acid

Page 19

It can be seen that two hydrogen bonds would be expected to bring about more stabilization than one
hydrogen bonds.

1
2

O
C

1
2

1
2

O
C

1
2

1
2

1
2

H
O

H
O

H
O

Including ortho effect, the order of acidity of some substituted benzoic acids is given as:
(a) onitro benzoic acid > pnitrobenzoic acid > mnitro benzoic acid > benzoic acid.
(b) omethyl benzoic acid > benzoic acid > mmethyl benzoic acid > pmethyl
benzoic acid
(c) omethoxy benzoic acid > mmethoxy benzoic acid > benzoic acid > pmethoxy benzoic acid.

Illustration 3
Question:

Explain why acrylic (propenoic) acid is weaker acid than propynoic acid?
O +

Solution:

O +

CH2 = CH C O H
sp2

CHC C OH

sp2

Propynoic acid

Acrylic acid

If we look at these two acids, electron withdrawing effect of sp 2 carbon adjacent to carbonyl group in
acrylic acid is less than the electron withdrawing effect of sp hybridized carbon. Thus, OH bond of
propynoic acid has greater polarization than the OH group of propenoic acid. Hence, propynoic acid is a
stronger acid than propenoic acid.

Account for the fact that salicylic acid, oHOC6H4CO2H is a stronger acid than
oCH3OC6H4CO2H.
A CH2 group flanked between two electron withdrawing groups has acidic hydrogen. Aldehydic group is
more electron withdrawing than ketonic group, which is more electron attracting than ester groups. Thus, order
of acidity of carbon acids is

HCCH2CH > CH3CCH2CCH3 > CH3OCCH2COCH3


O

Cl
CHCl3 is more acidic than CHF3 because the conjugate base of CHCl3 i.e. :CCl is stabilised by I

Cl
effect of Cls as well as by pd delocalization (which is absent in :CF3 due to the absence of dorbital in F).
For the same reason, S

8.3

S is more acidic than O

O.

BASIC STRENGTH OF ORGANIC BASES

Strength of bases is related to the ease of accepting a proton, which in turn depends on the availability
of electron pair on the nitrogen atom (or some other basic atom). More is the availability of electron pair, more
easily
the
proton
will
be
accepted
and
more
will
be
the
basic
strength.
If we compare the basicities of NH3, MeNH2, Me2NH and Me3N, then at a glance it would
seem like NH3 < MeNH2 < Me2NH < Me3 N is the basicity order but the result is quite different in aqueous
media. The correct order is Me2NH > MeNH2 > Me3N > NH3. This order can be
explained considering the solvation effect of the protonated amines. But in absence of a polar protic solvent
i.e. in the presence of nonpolar solvent or gaseous phase, the order of basicity is Me 3N > Me2NH > MeNH2 >

Page 20

NH3. Tetraalkylammonium salts, e.g. R 4NI on treatment with moist silver oxide (AgOH) yield basic solutions
comparable in strength with the mineral alkalis. This is readily understandable as R 4N OH formed is
completely ionized to give R 4N and free OH.The effect of introducing electronwithdrawing groups, e.g. Cl,
NO2, close to a basic centre decreases the basicity, due to their electronwithdrawing inductive effect. Thus
the amine Tris (trifluoro methyl) amine is found to be virtually nonbasic due to the presence of three powerful
electronwithdrawing CF3 groups.
F3C

F 3C
F 3C

N:

The amides are also found to be only very weakly basic in water because of the I and R effect of
RCO group which makes the electron pair very slightly available on nitrogen atom.

O
RC

..

NH2

RC=NH2

If two C=O groups are present, the resultant imides often become sufficiently acidic to form alkali metal
salts. For example, benzene1,2dicarboximide is not basic but is acidic in nature because of the presence of
two electronwithdrawing >C=O groups.
O

OH
H2O

N
O

In aniline, owing to resonance, the lone pair of electrons on the nitrogen atom is less available for
coordinating with a proton and at the same time, small positive charge on the nitrogen atom would tend to
repel a proton. Alternatively, since there are more resonating structures possible for aniline itself than for the

cation C 6H5 NH3 , the former will be stabilized with respect to the latter.

..

NH2
NH2
NH2
NH2
..
..

..
NH2

..
Aniline is a weaker base than ammonia or cyclohexylamine. It is because of the fact that the electron
pair on nitrogen is involved in delocalization, making it less available for donation.
..

NH2
..

NH3
cyclohexylamine

ammonia

Diphenylamine is even a weaker base than aniline due to the presence of another phenyl group
..

NH

and triphenylamine (Ph3N) is not basic at all by any means.Introduction of alkyl group (like Me) on the
nitrogen atom of aniline results in small increase in the basic strength.
C6H5 NH2 < C6H5 NH2 Me < C6H5NMe2
Unlike such introduction in aliphatic amines, this small increase in basic strength is progressive,
indicating that cation stabilization through hydrogenbonded solvation, here has less influence on the overall
effect.

Page 21

The effect of a ring substituent on basicity depends on whether the substituent is electron attracting or
releasing, its ability to enter into resonance with the aminogroup and its position. All the nitroanilines are
weaker bases than aniline. The nitrogroup has a strong R effect and o and p nitroaniline are therefore,
more resonance stabilised than aniline itself.
O
O
..
+
+
+
NH2
N
NH2
N

A mnitro group cannot enter into resonance with the aminogroup, but nevertheless mnitroaniline is
a much weaker base than aniline. In this case, nitrogroup has a strong I effect. This I effect tends to draw
into
the
ring
the
lone
pair
of
N,
thus
decreasing
its
basicity.
Thus, the order of basicity of nitroanilines is C 6H5NH2 > mNO2C6H4NH2 > pNO2 C6H4 NH2 > oNO2C6H4NH2.
..

O
O
O
NH2
NH2
NH2

O=N
O=N .
ON
.
so on

..
NH2

NH2

NH2

NH2

..
so on

..
N

N
N
O
O
O
O
When the ring contains an electronreleasing group, this reduces resonance of the
NH2 group with the ring and consequently should increase basicity. The methyl group raises the electron
density more at the o and ppositions than at the mposition. Thus, the carbon atom para to the methyl group
has a high electron density and the lone pair on the nitrogen atom is therefore prevented to some extent from
entering into resonance with the ring. A methyl group raises the electron density at the m position only to a
very small extent. Hence, resonance with the ring of NH2 group at this position is prevented less than for the
pposition. Consequently, a methyl group in the ring increases the basicity of the aniline, more so from the
pposition than from the mposition. Thus, order of basicity of methyl anilines is pCH3C6H4NH2 >
mCH3C6 H4NH2 > C6H5NH2 > oCH3C6 H4NH2.
O

The pOMe group has a +R effect and its presence increases basicity. In the mposition,
it can exert only a I effect and this decreases the basicity. The order of basicity of methoxy anilines is
pCH3OC6H4NH2 > C6 H5NH2 > oCH3OC6H4NH2 > mCH3OC6H4NH2 .
..
..
..
..
NH2 ..
NH2
NH2
NH2
OMe
OMe
OMe
OMe
..
etc.
..
..
..
NH2

OMe
..
NH2

..
NH2

..
NH2
..

..
:OMe

..
NH2
..

OMe

OMe

etc.

OMe

Page 22

Compare the basicities of PhNH2, Ph2NH and cyclohexyl amine.

Illustration 4
Question:

Compare the basicities of following compounds:


..
N
H
(I)

Solution:

..
N

..
N

.N.
(II)

(III)

(IV)

In pyrrole( I), the lone pair on nitrogen is involved in resonance, while in other three, it is not involved. So,
(I) is least basic. Among ( II), (III) and ( IV), the lone pair on nitrogen in ( II) lies in sp2 hybrid orbital (which

is smaller than sp 3 hybrid orbital and is held more strongly by the nucleus, so the electron pair is less
available for donation), while in ( III) and ( IV) it lies in sp 3 hybrid orbital. Among ( III) and ( IV), ( III) has
greater electron releasing groups by induction (+ I) than ( IV). So, the correct order of basicity is
(III) > (IV) > (II) > ( I).

9. STERIC INHIBITION OF RESONANCE


We find many a times that due to steric reasons (the repulsion between the bulky groups), the
resonance phenomenon in hindered, which might otherwise be possible if there is no loss of planarity of the
group. For example, let us compare the acidity of 3,5dimethyl 4nitrophenol and 2,6dimethyl 4nitrophenol.
The explanation is neighbouring methyl groups will repel the bulky nitro group and consequent planarity of the
participating orbitals of N, (which is 2pz) is lost hence less stabilization of the conjugate base by resonance
takes place.But in the case of other isomer no such steric interaction is observed. Thus, the corresponding
conjugate base is stabilized through extensive delocalisation of negative charge to the oxygen of NO 2 group.

CH3

CH3

HO

..
H+ + O

CH3

..
O

N
CH3

O
O

..

CH3

CH3

CH3

CH3

CH3

CH3
..

CH3
CH3

CH3

.. N

O
O

CH3

Steric reasons also play important role in determining the basicity of aromatic amines.
For example, 3,5 dimethyl4nitro aniline is more basic than 2,6 dimethyl4nitro aniline. On the same
argument as stated above, it can be said that lone pair of NH2 group cannot go to the apparently available
NO2 group by conjugation in 3,5dimethyl4nitroaniline.

Account for the fact that (a) 4cyanoaniline is slightly more basic than 4nitroaniline and
(b) 3, 4, 5trinitroaniline is more basic than 4cyano3, 5dinitroaniline.

10. TYPES OF ORGANIC REACTIONS


Organic reactions can be classified into the following categories:
(i) Substitution reactions

Page 23

(i)

(ii) Addition reactions


(iii) Elimination reactions
(iv) Rearrangement reactions
Substitution Reactions:

A reaction in which one group or atom is replaced by another is called a substitution reaction. The
incoming group is bonded to the same carbon to which the leaving group was bonded. The substituting
species may be either a nucleophile, an electrophile or a free radical.
As for example,
..

..

..

:
: :
HO
.. + CH2Br: HOCH2 + Br
..
CH3
CH3
Nucleophile 1 alkyl halide

(ii)

Substitution product

Addition Reactions:

A reaction in which the reagent is added to the substrate to form a product is called addition reaction. It
is characteristic to compounds containing multiple bond (>C=C<, CC, >C=O, CN etc.). The reactivity of
these compounds is due to the loosely held electrons which are particularly available to a reagent that is
seeking electrons like an electrophile or a free radical.As for example, hydrogen halides (HCl, HBr and HI) add
to the double bond of alkenes.

R
CC

C = C + HX

X H
Mechanisms for addition of hydrogen halide to an alkene involves the following two steps:
Step 1.

R H

Slow
(RDS)

C = C + HX

CC +X

Step 2.

CC + X

Fast

CC
X H

The addition of HBr to some alkenes give a mixture of the expected alkyl bromide and an isomer
formed by rearrangement.
CH3

CH3
CH2=CHCHCH3

CH3

Br

CH3CHBrCHCH3
2Bromo3methylbutane

CH3CHCCH3

1,2Hydride shift

CH3
CH3CH2CCH3

Br

CH3
CH3CH2CCH3
Br
2Bromo2methylbutane

(iii)

Elimination Reactions:

When two atoms or groups from adjacent carbons are eliminated with the formation of unsaturated
compounds (alkene or alkyne), the reaction is called elimination reaction. Most commonly a leaving group
(from the carbon) and a proton from the carbon are eliminated. Hence, the reaction is known as 1,2 or
, elimination or simply elimination.As for example, dehydrohalogenation of alkyl halides with alcoholic
solution of KOH.

Page 24

H C C H KOH(alc) H C C H KBr H2O

Br

Ethyl bromide

Ethylene

(iv) Rearrangement Reactions:

It involves the migration of an atom or a group from one atom to another within the molecule. The type
of migration depends on the number of electrons the migrating atom or group carries with it. The most
common type are 1,2rearrangements in which the migrating group moves to the adjacent atom with its
bonding pair of electron (nucleophilic rearrangement or anionotropic rearrangement).
M
M
AB

AB

Migration terminus

Migration origin

The group may move without the bonding pair (cationotropic rearrangement) or with a single electron
(free radical rearrangement) and may not be 1,2 but longer rearrangements. As for example, 1chlorobutane
rearranges to form 2chlorobutane when heated in the presence of anhydrous AlCl3 at 573K.

CH3CH2CH2CH2Cl

Anhyd. AlCl3
573 K

CH3CHCH2CH3

1-Chlorobutane

Cl
2-Chlorobutane

11. AROMATICITY
Planar monocyclic rings containing (4n + 2) electrons (where n = 0, 1, 2, 3, and so on), should be

aromatic. This is known as Huckel


' s rule for aromaticity. Applying this rule, benzene and its derivatives have
six delocalised electrons and n = 1.
Thus to be aromatic, a molecule must have 2(n = 0), 6(n = 1), 10(n = 2) etc. electrons in a closed
orbital loop. Another requirement for aromaticity is planarity of the ring. If the ring is not planar, overlap of
porbitals is diminished or prevented, then compound will not be aromatic.
Derivatives of benzene are aromatic as they fulfill both the conditions. Molecules having two or more
benzene rings fused together are called polycyclic benzenoid aromatic hydrocarbons. For example,
naphthalene, anthracene etc.

Naphthalene, n = 2
Number of electrons = 10

Anthracene, n = 3
Number of electrons = 14

Nonbenzenoid aromatic compounds are those which contain a ring that is not six membered. For
example, cyclopentadienyl anion, cyclopropenium cation, tropylium cation etc.

Cyclopropenyl cation
(n = 0)

Cyclopentadienyl anion
(n = 1)

Tropylium cation (Cycloheptatrienyl cation)


(n = 1)

Cyclopentadiene is not aromatic as it does not obey (4n + 2) Huckel rule and also the
electrons cannot be delocalized because of the tetrahedral CH2 group. When a proton is removed from this
carbon atom, it becomes sp2 hybridised and thus delocalization is permitted. Thus, this anion becomes aromatic in
nature. Cycloheptatriene has six electrons but the CH2 group prevents delocalisation. When a hydride ion is

Page 25

removed from this carbon atom, a vacant porbital is created, which makes the carbon atom sp2 hybridised
and thus cation becomes aromatic in nature.
Cyclic conjugated compounds, which possess only 4n electrons, do not satisfy the Huckel rule and are
antiaromatic in nature.

Cyclopropenyl anion

Tropylium anion

Cyclopentadienyl cation

In cyclic compounds, when an element other than carbon is present in the ring, they are called heterocyclic
compounds. They are aromatic in nature because of fulfilling both the conditions.

..
N
|
H

N
..
Pyridine

Pyrrole

..
O
..

..
S
..

Furan

Thiophene

In pyrrole, furan and thiophene, the lone pairs in sp3 hybrid orbitals are involved in resonance with the ring

bonds to form the aromatic sextet (4n + 2) electrons. In pyridine, the lone pair is in sp2 hybrid orbital, which is
not involved in delocalization. Thus, pyridine also has 6 electrons and is aromatic in nature.

Write the product of following reaction?


H

H
2C4H9Li

Illustration 5
Question:

Write the products of the reaction or the things indicated against it.
KOH

(a)

AgNO3

(c)

Solution:

(b)

(The direction of dipole moment)

Sometimes during a reaction, if there is possibility of formation of 2 or more products, of which one of them
shows aromatic character, then that product is the preferential product.
(a)

+ H2O
H

(b)

(c)

..

NO3 + AgI

Page 26

SOLVED SUBJECTIVE EXAMPLES


Example 1:
State which interactions are preferable and write the probable products of the following reactions.

CH2CCH3 + :OH

CH2 C CH3 + :OH or


H
O

(i)

(ii)

OH

O O

(iii)

O O

..

C C

H +

or

C C
..
OH

:S H
or

..
OH
O

CH3
CH3C
+

(iv)

OH

:S

O
or
CH3C

CH3
:OS
O

OH

Solution:
(i) As OH is a hard base it will prefer to abstract proton, which is a hard acid in this situation.
The product is CH2COCH3 in equilibrium with CH3COCH3 and OH.
(ii) Here OH is acting as a neucleophile as there is no acidic hydrogen available in the molecule. The product is
OH

thus

in equilibrium with the reactants.

C C

O O

(iii) OH is a hard base but SH is a soft base. Obliviously OH will prefer to bind with proton (H+) more readily
than HS. The product is H2O at equilibrium.
(iv) S

is a soft base. Hence, it will prefer to attack the soft acid C of carbonyl carbon.
CH3

The product is CH3CSO3H in equilibrium with the reactants.


O

Example 2:
Why do electrophiles attack trichloromethyl benzene at meta position where as they attack benzene ring
at ortho and para position in chloromethyl benzene?

Solution:
Participation of chlorine atoms in H (Hyperconjugation).

Example 3:
CH3Cl + AgCN Major product + Minor product. Describe the major product with reasoning.

Page 27

Solution:
CH3NC. This is because of hard acidhard base interaction (nitrogen atom is a harder acid than carbon).

Example 4:
Arrange the following electrophiles in the decreasing order of electrophilicity?
O2N

NO2

OMe

N2

N2

N2

(II)

(I)

(III)

Solution:
(III) is the strongest electrophile because of R effect of nitro group is also operative along with its I effect but
(II) has a greater +R effect (lesser I effect) and in (I) NO2 from meta position will only show I effect. Thus, the
decreasing order of electrophilicity is (III) > (I) > (II).

Example 5:
(a) If the pKa of an acid is 6, what will be the pK b of its conjugate base?
(b) Which of the following hydrocarbon is most acidic?
CH3
(i)

(ii)

(iii)

(iv)

Solution:
(a) pKa = 6, pKb of its conjugate base = 14 6 = 8.
(b) Cyclopentadiene is most acidic as the loss of proton in it gives a carbanion, which is stabilized by aromaticity.
..

+ H+

(i)

Most stable (aromatic)

..

+ H+

(ii)
CH3

.. CH2

+ H+

(iii)
..

(iv)

+ H+

In case (i), the equilibrium is shifted most in the forward direction, hence compound (i) is most acidic.

EXERCISE I
AIEEE-SINGLE CHOICE CORRECT
1.

Consider the following amines:


(1) C6 H5NH2
(2) oNO2C6 H4NH2
(3) mNO2C6H4NH2
(4) pNO2C6 H4NH2
Arrange these compounds in decreasing order of basicity:
(a) (1) > (2) > (3) > (4)
(b) (2) > (1) > (3) > (4)
(c) (1) > (3) > (4) > (2)
(d) (1) > (3) > (2) > (4)
Page 28

2.

Weakest base among the following amino compounds is:


NH

(a)
(c)
3.

(d)

NH2

Most acidic hydrogen is present in:


O

(a)

4.

NH

(b) NH

(b)

(c) (CH3CO)3CH
(d) (CH3)3COH
Which nitrogen in Lysergic acid diethylamide (LSD) is most basic?
O

(1)

HN
(2)

(3)

CN(C2H5)2

N
CH3

5.

(a) 1
(b) 2
(c) 3
(d) All are equally basic
Which of the following carbanion is most stable?
CH2

CH2

CN

NO2

(a)

(b)

(c)
NO2

6.

7.

CH2

CH2

(d)
CN

Which one of the following compound is most acidic?


(a) HOCH2COOH
(b) O2NCH2COOH
(c) ClCH2COOH
(d) NCCH2COOH
Arrange homolytic bond energies of CH bonds designated by (I), (II), (III), (IV) and (V) in increasing
order.
(II)
(V )

(I)

H
(III)

H
CH2H
(IV)

8.

9.

(a) (II) < (V) < (IV) < (III) < (I)
(b) (III) < (V) < (IV) < (II) < (I)
(c) (I) < (III) < (IV) < (II) < (V)
(d) (II) < (IV) < (V) < (I) < (III)
Consider the following three halides
(A) CH3CH2Cl (B) CH2=CHCl (C) HCCCl
Arrange these three compounds in decreasing order of CCl bond length.
(a) (A) > (B) > (C)
(b) (C) > (B) > (A)
(c) (B) > (C) > (A)
(d) (A) > (C) > (B)
Arrange basicity of the given compounds in decreasing order.
(A) CH3CH2NH2 (B) CH2=CHNH2 (C) CHCNH2
(a) (A) > (B) > (C)
(b) (A) > (C) > (B)
Page 29

10.

(c) (C) > (B) > (A)


(d) (B) > (C) > (A)
Which of the following is a nonaromatic compound/species?

(A)

(B)

(C)

(D)

11.

12.

(a) (A)
(b) (B)
(c) (C)
(d) (D)
Arrange stability of given compounds in decreasing order
(1) C6 H6
(2) CH2=CHCH2 CH2CH=CH2
(3) CH2=CHCH=CH2
(4) CH2=C=CH2
(a) (3) > (1) > (4) > (2)
(b) (1) > (3) > (2) > (4)
(c) (1) > (3) > (4) > (2)
(d) (3) > (1) > (2) > (4)
The most stable free radical is
Me

(a)

13.

(b)

(d)

According to the Huckels rule, which of the following species will be aromatic?

(I)

14.

(c)

(II)

(III)

(IV)

(a) (I)
(b) (II)
(c) (III)
(d) (IV)
Which of the following compound is most acidic?
OH
NO2

(a)

OH

(b)
OH

OH

(c)

(d)
NO2
NO 2

15.

Which of the following carbocation is most stable?

(a) (CH 3 ) 2 CH

(c) Ph CH CH3

(b) (CH 3 )3 C

(d) Ph CH2

EXERCISE II
IIT-JEE- SINGLE CHOICE CORRECT
1.

Identify the species not capable of acting as an electrophile.


Page 30

2.

(a) BCl3
(b) AlCl3

(c) NH 4
(d) CO2
Which of the following species is a nucleophile but not an electrophile?

(a) NH 4

(b) NH 3 OH

(c) H3 O

(d) CH3CCH3
O

3.

Which is the most stable carbocation?


(a) (CH3)2 CH+

4.

CH2

(c) CH 2 CH CH 2
(d) (CH3)3C+
Steric inhibition of resonance can be expected in
(a)

(b)

(c)
5.

(b)

(d)

(b)

CH2

Which free radical is the most stable one?

CH2

(a)

NO2

(c) (CH3)3C

(d) (CH3)2CH

6.

7.

8.

9.

In (tBu) 3C, the hybridization of central carbon atom is


(a)Hsp
(b) sp2
(c) sp3
(d) none of these
Which of the following represents the correct order of acidic strength?
(a) HCO2H > CO2HCO2H
(b) CH3CO2H > HCO2 H
(c) CO2HCO2H < CO2HCH2 CO2H (d) CO2HCO2H > HCO2H
A compound/species is antiaromatic when it has
(a) 4n electrons
(b) (4n + 1) electrons
(c) (4n + 2) electrons
(d) (4n + 3) electrons
The cyclopropenyl cation,

is

(a) aromatic
(c) nonaromatic

(b) antiaromatic
(d) non planar

10.

11.

The cyclopentadienyl cation,

is

(a) aromatic
(b) antiaromatic
(c) nonaromatic
(d) none of these
In which of the following molecule, the group attached to benzene donot show any type of resonance
effect?
Page 31

12.

13.

14.

(a)

NH2

(b)

NH3

(c)

OH

(d)

Cl

Which of the following is correct order regarding the acidity of carboxylic group?
(a) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH
> ClCH2CH2CH2COOH
(b) CH3CH2CH(Cl)COOH < CH3CH(Cl)CH2COOH
< ClCH2CH2CH2COOH
(c) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH
< ClCH2CH2CH2COOH
(d) CH3CH2CH(Cl)COOH < CH3CH(Cl)CH2COOH
> ClCH2CH2CH2COOH
Which of the following is correct order regarding I effect of the substituents?
(a) NH2 > OH > F
(b) NH2 < OH < F
(c) NH2 > OH < F
(d) NH2 < OH > F
Which of the following order is not the correct order regarding I effect of the substituents?
(a) I < Cl < Br < F

(b) NR2 < O R 2

15.

16.

(c) NR2 < OR < F


(d) SR < OR < OR 2
Which of the following is correct order regarding the acidity of carboxylic acids?
(a) (CH3)3 CCOOH > (CH3 )2CHCOOH > CH3CH2COOH
(b) (CH3)3 CCOOH > (CH3 )2CHCOOH < CH3CH2COOH
(c) (CH3)3 CCOOH < (CH3 )2CHCOOH > CH3CH2COOH
(d) (CH3)3 CCOOH < (CH3 )2CHCOOH < CH3CH2COOH
Which of the following compound has the highest pKa value?
OH

OH
Cl

(a)

NO2

(b)
OH

OH
OCH3

CH3

(c)
17.

(d)

Which one of the following compound would you expect to be the strongest carbon acid?
O

(a) CH2(COOC2H5 )2

(b)
O

(c) CH3COCH2COOC2 H5
18.

(d)

Which is the most stable singlet carbene among the following?


..

(a) CF2
..

19.

..

(b) CCl2
..

(c) CBr2
(d) CI2
Which of the following species cannot function as an electrophile?
..

(a) HCl

(b) CCl2

(c) SiF4

(d) H3O
Page 32

20.

Which of the following nitrogenous base is the strongest in water?


(a)

(b)
N

(c)

(d)
N

21.

22.

In which one of the following compounds delocalisation is not possible?


(a) 2butene
(b) 1,3butadiene
(c) 1,3,5hexatriene
(d) Benzene
Consider the following carbocations:

(1) CH3CH2

(2) CH2=CH

(3) CH2=CHCH2

(4) C6H5CH2

Stability of these carbocations in decreasing order is

23.

(a) (4) > (3) > (1) > (2)


(b) (4) > (3) > (2) > (1)
(c) (3) > (4) > (2) > (1)
(d) (3) > (4) > (1) > (2)
Which one of the following cation is most acidic?

NH3

NH3

(a)

(b)
O

NH3

NH3

(c)

(d)
NO 2

24.

CH3

Which of these species is capable of acting as electrophile?


(a) CO2
(b) CH3CH
O

25.

(c) AlCl3
(d) All of these
Decreasing order of stability of given carbocations is

(1)

(2) CH2=CHCH2

(3) C6H5CH2

(4) CH3CHCH3

(a) (3) > (2) > (4) > (1)


(c) (1) > (3) > (2) > (4)

(b) (1) > (3) > (4) > (2)


(d) (3) > (2) > (1) > (4)

EXERCISE III
MORE THAN ONE CHOICE CORRECT
1.

The correct order of the stability of the given resonating structures


Page 33

CH2CHCH=CHOCH3
(I)

CH2CH=CHCH=OCH3
(II)

CH2=CHCHCHOCH3
(III)

2.

CH2=CHCHCH=OCH3
(IV)

(a) (IV) > (II) > (I) > (III)


(b) (IV) > (II) > (III) > (I)
(c) (III) < (I) < (II) < (IV)
(d) (I) < (III) < (II) < (IV)
Which of the following compound shows +R effect?
O
OCH3

NHCCH3

(a)
3.

(b)

(c)

(d)

Which of the following reaction leads to the formation of carbocation as an intermediate?

C N; polar

(a) RCl ?

(b) RH + X2 ?

protic solvent

4.

C(CH3)3

(c) RCH=CH2 + H ?
(d) CH3NO2 + B ?
Which of the following are aromatic species?
(a)

..

(b)

..

(c)

(a)

(b)

HO2C

CO2H

5.

NH3

(d)
..

The correct acidity order of the indicated groups in the following compound is

(c)

6.

7.

(a) (b) > (a) > (c)


(b) (a) < (b) < (c)
(c) (c) > (b) > (a)
(d) (c) < (a) < (b)
Which of the following is true about carbenes?
(a) Carbenes can be formed by elimination of CHCl 3.
(b) Carbenes can undergo nucleophilic attack.
(c) Among alkylated carbenes, singlet form is more stable than triplet form.
(d) Carbenes can undergo addition to double bond to give cyclopropyl systems.
In which of the following molecules all the effects namely inductive, mesomeric and hyperconjugation
operate:
Cl

(a)

COCH3

(b)
CH3

CH3

(c)

(d) CH3CH=CHCl

CH3

8.

Which of the following reaction intermediates are electrophilic in character?


(1) Carbocation
(2) Carbanion
(3) nitrenes
(4) Carbenes
(a) (2) and (4)
(c) (3) and (4)

(b) (1) and (3)


(d) (1) and (4)
Page 34

9.

is more basic than

because
..
N

N
..

(a)

is a six membered aromatic ring.


N
..

(b) Lone pair of

is not taking part in delocalization.


N
..

(c) Lone pair of


(d)
10.

..
N

is taking part in delocalization.

is an aromatic amine.

..
N

Which of the following compound/species is an aromatic species?


O

(a)

(b)
O

(c)
11.

(d)

Which of the following represents right order of acidity?


(a) CHF3 > CHCl3
(b) CHCl3 > CHF3
(c)
O

12.

13.

>

(d)

>
O

Which of the following intermediate is electrically neutral?


(a) Carbanion
(b) Benzyne
(c) Carbene
(d) Carbocation
Which of the following intermediate is aromatic in nature?
CH3

(a)

(b)
:

(c)

(d)

(singlet)

..

14.

Which of the following is a correct statement?


(a) Aniline shows stronger resonance than phenol.
(b) 2,6dimethyl4nitrophenol is more acidic than 3,5dimethyl4nitrophenol.
.

(c) CH2CH=CHCH2 is a valid resonance structure of CH2=CHCH=CH2.


15.

(d) Benzyl free radical is more stable than tbutyl free radical.
In which of the following pairs, first member is more stable than the second?

.
(a) (C6H5 )3 C , (C6H5 ) 2 C CH 3
(b) :CH2, CH2
.

(c) (C6H5)3C: , :CH3

(d) (C2H5 )3 C, (CH 3 )3 C


Page 35

EXERCISE IV
MATCH THE FOLLOWING
1.
Column I

I.

Elimination

Column II
(A)

R
+ HX CC

C=C

X H

II.

Substitution

(B)

CH3CH2CH2Cl

Anhydrous
AlCl3,

CH3CHCH3
Cl

III. Rearrangement

(C)

CCC

XY

IV. Addition
(D)

(E)

+ HNO3

RCO2Ag + X2

C
C

H2SO4

CCl4

NO2
+ H2O

RX + AgX + CO2

2.
Column I

I.

II.

Cl

Column II

SbCl5

(A)

NO3 + AgCl

Cl4Sb

Cl

(B)
Cl

Cl

III.
Br

IV.

AgNO3

2AgBF4

(C)

(D)

BF4

BF4

SbCl6

+ 2AgBr

Br
(E)

.
H . K
3.

Match the following pKa values if pKa value of orthonitro aniline is 0.29
Column I

Column II

I.

Paramethyl aniline

(A)

3.98

II.

Paramethoxy aniline

(B)

5.19

Page 36

III. Paranitro aniline

(C)

0.39

IV. Parachloro aniline

(D)

1.02

(E)

5.29

1.

ASSERTION AND REASON TYPE


Direction: Read the following questions and choose
(A) If both Assertion and Reason are true and Reason is the correct explanation of the assertion
(B) If both Assertion and Reason are true but Reason is not correct explanation of the Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
Assertion: The basic strength of amines in an aqueous solution is (CH 3)2 NH > CH3NH2 > (CH3)3 N >
NH3 .
Reason:

2.

(a) (A)
(b) (B)
(c) (C)
(d) (D)
Assertion: The ohydroxy benzoic acid is a stronger acid than omethoxy benzoic acid.
Reason:

3.

O group shows +I effect while OH group shows I effect. +R effect is shown by O as


well as OH group.

(a) (A)
(b) (B)
(c) (C)
(d) (D)
Assertion: Maleic acid is a weaker acid than fumaric acid towards first ionization.
Reason:

5.

The ortho effect is more prominent in ohydroxy benzoic acid than in omethoxy benzoic
acid.

(a) (A)
(b) (B)
(c) (C)
(d) (D)
Assertion: Phenoxide ring is more activating than phenol ring towards electrophilic substitution reaction.
Reason:

4.

The basic strength of amines in aqueous solution is governed by the availability of electron
pair on nitrogen as well as on the solvation of their conjugate acids.

Conjugate base of maleic acid is stabilized by intramolecular hydrogen bonding but not the
conjugate base of fumaric acid.

(a) (A)
(b) (B)
(c) (C)
(d) (D)
Assertion: 7bromo1,3,5Cycloheptatriene ionizes more readily than 5bromo13cyclopentadiene.
Reason:
(a) (A)

Cycloheptatrienyl cation is more stable than cyclopentadienyl cation due to aromatic


character of the former.
(b) (B)
(c) (C)
(d) (D)

PASSAGE BASED PROBLEMS


Planar monocyclic rings containing (4n + 2) electrons (where n = 0, 1, 2, 3, and so on), should be

' s rule for aromaticity. Applying this rule, benzene and its derivatives have
aromatic. This is known as Huckel
six delocalised electrons and n = 1.
Thus to be aromatic, a molecule must have 2(n = 0), 6(n = 1), 10(n = 2) etc. electrons in a closed orbital
loop. Another requirement for aromaticity is planarity of the ring. If the ring is not planar, overlap of porbitals is
diminished or prevented, then compound will not be aromatic.
Derivatives of benzene are aromatic as they fulfill both the conditions. Molecules having two or more benzene
rings fused together are called polycyclic benzenoid aromatic hydrocarbons. For example, naphthalene, anthracene etc.

Nonbenzenoid aromatic compounds are those which contain a ring that is not six membered. Examples
of such compounds are cyclopentadienyl anion, cyclopropenium cation, tropylium cation etc. Cyclic conjugated
Page 37

compounds, which possess only 4n electrons, do not satisfy the Huckel rule and are antiaromatic in nature. In a
reaction the reactant would tend to react with reagents that can result into aromatic products / salts.
1.
Which of the following is the correct option regarding the direction of the dipole moment?

2.

(a)

(b)

(c)

(d)

Which of the following is the correct statement?


(a)

Br

(b)

3.

Br gives an immediate turbidity with aqueous AgNO3 .

(c) Both of them give immediate turbidity with aqueous AgNO 3.


(d) None of them give any turbidity with aqueous AgNO3 .
Which of the given statement is correct?
is more acidic than CH2=CHCH2CH=CH2

(a)
(b)

4.

gives immediate turbidity with aqueous AgNO3.

is more acidic than

(c) Both (a) and (b) are correct.


(d) None of the given option is correct.
Which of the given reaction is correct?
(a)

O + HBr

(b)

O + HBr

Ph

Ph

(c)

OH
Br
OH
Br

Ph
+ HClO4

Ph

ClO4

OH

(d) Both (a) and (c) are correct.

EXERCISE V
SUBJECTIVE PROBLEMS
H O

O
H

1.

In H

, which hydrogen is the most acidic? Explain your choice.

CH3

2.

OH
CH2

C
O

(I)

OC2H5
,

CH3
C

CH2

CH3

O
(II)

Page 38

When (I) and (II) are treated with base, separately carbanion results. Which carbanion will be more
stable?
basicity

order

of

the

The

4.
5.

Explain the order.


CH2=CHCl does not give CH2 =CHOH easily on treatment with OH. Explain.
HCl
CHCH

CH2=CHCl
HCl

is

<

N .

ClCH2CH2Cl
Possibility2

Possibility1

7.

compounds

HCl

CH3CHCl2

6.

following

3.

In the above reaction sequence if carbocation formation is the intermediate step, then out of the two
possibilities, which one will be favoured?
..
..
Between, C = C F and C = C Cl , which lone pair conjugation will be more preferred?
Give proper explanation/s for the following:
(a) Compound I has greater dipole moment than compound II.

Ph
O

Ph

Ph

Ph

II

(b) Which compound has the greater electron density on its nitrogen atom?

or

NH

N
H
(c) Species I is more stable than II.

I
8.

II

Give proper explanation/s for the following:


(a) A methyl group bonded to benzene loses proton more readily than a methyl group bonded to
cyclohexane.
(b) The direction of the dipole moment in fulvene and calcene.

fulvene

calcene

(c) Compound I is more stable than the compound II.

9.

I
II
(a) Which of the two enols would you expect to be the stronger acid and why?

Page 39

O
H3C

OH

CH2
H3C

OH

CH3
O

is basic but

(b)
N

(c)

NH

is more acidic than


O

OH

(d)

is not.

is less basic than

10.

OH

The phenols shown below have approximate pKa values of 4, 7, 9, 10 and 11. Suggest with
explanations, which pKa value belongs to which phenol?
OH
OH

OH
O2N

OH

OH

O2N

NO2

OH

ANSWERS
EXERCISE I
AIEEE-SINGLE CHOICE CORRECT
1. (c)

2. (d)

3. (c)

4. (b)

5. (a)

6. (b)

7. (a)

8. (a)

9. (a)

10. (d)

11. (b)

12. (d)

13. (b)

14. (d)

15. (c)

EXERCISE II
IIT-JEE-SINGLE CHOICE CORRECT
1. (c)

2. (b)

3. (d)

4. (c)

5. (a)

6. (b)

7. (d)

8. (a)

9. (a)

10. (b)

11. (b)

12. (a)

13. (b)

14. (a)

15. (d)

16. (d)

17. (b)

18. (a)

19. (d)

20. (d)

21. (a)

22. (a)

23. (c)

24. (d)

25. (c)

EXERCISE III
MORE THAN ONE CHOICE CORRECT
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1. (a, c)

2. (a, b, d)

3. (a, c)

4. (a, b, c)

6. (a, d)

7. (b, d)

8. (b, c, d)

9. (b, c)

11. (b, d)

12. (b, c)

13. (a, b)

5. (a, d)
10. (a, b, c)

14. (a, b, d)

15. (a, c)

EXERCISE IV
1.

MATCH THE FOLLOWING


I (C) ; II (D) ; III (B) ; IV (A)

2.

I (D) ; II (E) ; III (A) ; IV (C)

3.

I (B) ; II (E) ; III (D) ; IV (A)


ASSERTION AND REASON
1. (a)

2. (c)

3. (a)

4. (d)

5.

(a)

PASSAGE BASED PROBLEMS


1. (b)

2. (c)

3. (a)

4. (d)

EXERCISE V
SUBJECTIVE PROBLEMS
1.

COOH
always
(except SO3 H).

2.

Carbanion from (II) will be formed because of more thermodynamic stability due to greater resonance (as

shows

stronger

acidity

as

compared

to

other

functional

groups

COR group is more electron withdrawing than CO2R group).


3.
4.
5.

The basicity in the present case is influenced by solvation effect more than the availability of electron pair
on nitrogen atom.
This is because of lone pairp conjugation in CH2=CHCl increases the bond order between CCl bond.
Thus, CCl bond is not broken easily under milder conditions.

Possibility 1 will exist because CH2=CHCl on taking H+ from HCl form CH3CHCl , while in possibility II

the carbocation formed is CH2CH2Cl . The carbocation CH3CHCl is more stable than CH2CH2Cl
because the former has + I effect of CH3 , +R effect of Cl and I effect of Cl whereas the latter has I

effect of CH2 Cl. Thus, CH3CHCl is attacked latter by Cl to form CH3CHCl2 as the major product.
6.

Lone pairp conjugation between fluorine and carbon will be more effective than between chlorine and
carbon
(as
Cl
and
C
belong
to
3rd
and
2nd
period
respectively
and
F and C, both belong to 2nd period).
O
O
O

7.

(a)

I
Highly strained ring

The +ve charge is resonance


stabilized.

II

Page 41

Greater charge separation in I assigns it a higher dipole moment than II.


..

(b)

..

N H ; no such resonance is possible. Hence, electron density is more over nitrogen atom.

In
(c)

is

aromatic

as

it

involves

cyclic

delocalization

and

follows

Huckels

(I)

(4n + 2) e rule.
is not aromatic and hence is less stable.
(II)
CH3

CH3

8.

(a) In

, the CH bond is more polar than the CH bond in

due to e shift by

hyperconjugative effect. Moreover, the loss of H + gives benzyl carbanion PhCH2 , which is
resonance stabilized but not so in the anion of methyl cyclohexane.
(b)

CH2

CH2
aromatic

fulvene

aromatic
aromatic

calcene

Since both the charges have greater separation in calcene, so it has more dipole moment than fulvene.
The sp2 hybridised carbon is in a sixmembered ring where the angle strain will be less as

(c)
(I)

compared to that in

9.

where there is a fourmembered ring, which is more strained. Thus,

(II)
compound (I) is more stable than compound (II).
O
O
CH2
CH3
(a) H3C
H3C
OH
O
O

Both

and OH groups are in trans position and so no hydrogen bonding exists and can easily

tautomerise and it is more polar.


Page 42

H
O

CH3

H3C

CH3

H3C

Here, intramolecular hydrogen bonding exists and is less polar. This compound is more acidic than the
former as its carbanion is more resonance stabilized.
O
is basic but

(b)
N

is not because in the first case, the lone pair on nitrogen

NH

donot participate in resonance with


O since it will generate a double bond on bridgehead position
while in the second case it does participate in resonance, decreasing its basicity.
O

O
..
NH

(c)

NH

because its conjugate base is more resonance

is more acidic than


OH

OH

stabilized.
O

O
..

..

..

O
O

O
O

(d) The lone pair on nitrogen of

participates in resonance with phenyl ring, so it becomes

less basic. This doesnot happens in

.
N

OH
O

10.

NO2
(i)

(i) pKa = 4

OH

OH

OH

H
O
NO2
(ii)

(ii) pKa = 7

(iii)

(iii) pKa = 11

(iv)

(iv) pKa = 10

OH (v)

(v) pKa = 9

NO2 groups exerts I and R effect from ortho and para position. OH group exerts only I effect from
meta position. Me group exerts +I and +H effect from ortho and para position while it exerts only +I
effect from meta position.
Page 43