STRUCTURE AND BONDING 47

1.8.6 Resonance Vs. Inductive Effect

The more important points of difference between R ( or M) effect and 1-effect are listed in Table I.10.

Table 1.10: Difference between resonance and inductive effect

R (or M)- effect Inductive effect

1. Resonance effect involves
displacement o .Inductive effect involves drifting of
n
and n - electrons. electrons.

2. It operates
only in conjugated unsaturated 2. It operates in saturated compounds.
systems.
3. It does not involve delocalization of electrons
3. It involves delocalization of electrons.

4. Inductive effect involves slight drift of

4. Resonance effect involves complete transfer
electrons towards the more electronegative
of electron pair and hence full +ve and -ve atom and hence only partial charges (8' and
charges are developed. 8) are developed.

5. Resonance effects are transmitted over large 5. Inductive effects are transmitted only over
distances with almost no change in their short distances in saturated chains and the
magnitude. For
example, C3 of magnitude of the effect decreases rapidly
crotonaldehyde is equally susceptible to with number of
increasing intervening
addition of nucleophile as
C bonds.

CH-CH=CH-CHQ
4 3 2

l-CHCHCH:
4 3 2 1

CH-CH-CH= CH O:
4 3 2 1

1.8.7 Importance of Resonance Effects

Resonance effect plays key role in understanding the reactivity of organic compounds. Some important
uses of resonance effect are as follows:
1. Low reactivity of vinyl and aryl halides towards nucleophilic substitutions: In contrast to
alkyl halides, vinyl and aryl halides are much less reactive towards nucleophilic substitution reactions.
Reason: Both vinyl chloride and chlorobenzene can be regarded as hybrids of canonical forms I.
II and Ill and VI, respectively.
 48 ORGANIC CHEMISTRY vo
OL-
CHCH-CI
ch,cu
Vinyl chloride

:CI :C
:C

VI
IV

Due toChlorobenzene
the above resonance the carbon-chlorine bond acquires some double bond character.ththus
in a
Hence, the chlorine atom cannot be easily displaced in .

to carbon atom more tightly.

binding halogen
substitution reaction. halides undergo nucleophilic
benzyl halides: Allyl and benzyl
2. High reactivity of allyl and
than alkyl halides.
substitution reactions more readily resonance stabilized allyl and
halides undergo ionization to give
Reason: Both allyl and benzyl
benzyl cations.

lonization CHCH CH - H,-CH=CH,]+Br

CH=CH-CH-Br-
Allyl cation (Resonance stabilized)
Allyl bromide

CHBr CH CH2 CH CH CH2

lonization Br

Benzyl bromide
Benzyl cation (Resonance stabilized)

primary alkyl halides are not stabilized by resonance

In contrast, the carbocations obtained from
and hence are not formed easily.
3. Acid strength of carboxylic acids: The acid strength of the carboxylic acids depends upon
the ease of release of proton in aqueous solution to give carboxylate anion. Both carboxylic acids and
carboxylate anions are stabilized by resonance. Whereas canonical forms (lI nd IV) of carboxylate
anion are equivalent involving dispersal of negative charge, the canonical forms (I and I) of the
undissociated carboxylic acid are not only non-equivalent but also involve charge separation. we

know that resonance involving dispersal of negative charge makes greater contribution than resonance
involving separation of charge. Hence, the carboxylate anion will be more stable than carboxylic acid.
Hence, the acidic character of carboxylic acids.
 49
S T R U C T U R EA N D BONDING

R-C
R-C

C0-H

-H

R- R-C
II H
Carboxylic acid Carboxylic anion
(separation of charge) (dispersal of charge)

A Greater acidstrength of phenol compared to alcohols: In aqueous solution phenol releases

ion due to which it behaves as an acid. Any factor which renders phenoxide
a nroton to form phenoxide

than phenol will make phenol acidic.

ion more stable

0-H
H

Phenol Phenoxide ion

Both phenol and phenoxide ion by resonance. Whereas resonance of phenol involves
are stabilized
resonance involving dispersal
separation ofcharge, that of phenoxide involves dispersal of charge. Since,
of charge makes greater contribution than separation of charge, phenoxide
ion is more stable than

phenol. Hence, phenol is acidic in nature.

oH :OH :OH :OH

o

Phenol (separation of charge) less stable

:0
:0

teteeiaas

stable
Phenoxide ion (dispersal of negative change) more
 ORGANIC CHEMISTRY NOL-
not: stabilized1 by
50 ion both
esonance
are
alkoxide
molecule and the
alcohol
an phenols.
Contrary to this acids as
compared to
weak
lence,
alcohols are +H
R-0
R-0-
Alkoxide (lesSstable)
Alcohol (more stable) on oxygen
atom has hioh
higher enerp
charge
a formal
negative form
ion having to ionize and form less st
Moreover, the alkoxide very
low tendency
alcohols have
Therefore,
molecule.
than alcohol

alkoxide anion. are stronger

acids (K, = 105 to 10-10) than
than
alcohok
concluded that phenols formed by the release of
Thus, itmay
be
be due to the fact
that phenoxidethe
anion
prolon
10*). It may anion is not.
(K= 10 to but alkoxide primary amines:
by
1 phenol
amines
stabilized by
ise.g., ethylamine (K,
resonance

=5.6 x 10) of aliphatic

are much
and a r o m a t i c
stronger bases than aromatic 1° aminae
on iphati
relative base strength es
Comparison of
aniline5. (K, =4.2 x 10-). The +l-effect of ethyl group in ethylamine increases the electron densi,105)
to ammonia (K, =
1.8 y i
comparison
its base strength in
atom and
hence increases
the nitrogen
H

C.HN-H
+I effect of C2H; group
atom
Increased electron density at nitrogen
Stronger base
forms. Due to resonance the lone pair
Dai
of the following contributing
In contrast aniline is a hybrid benzene ring and is thus less readily availahi
atom gets
delocalized over the
of electrons on the nitrogen it is weaker base.
as compared to ammonia. Hence,
to capture a proton

NH

+R-effect of NH, group

(Decreased electron density at nitrogen atom)
is
and acetamide: Ethylamine (K, 5.6 1®) many
x =

6. Relative base strength of ethylamine

4.3 x 10-15). It may be due to folowing
reason:
imes stronger base than acetamide (K,
=

increases the electron density on the nitrogen

atom
In ethylamine, the +l-effect of ethyl group
due to which its base strength increases.

+1-efiect of C,H, group

CH N-H
(Increased electron density at nitrogen atom)
Ethylamine
(Stronger base)
 CH CL NH, CH-C=NH2
Acetamide +R-effect of amino group
Weaker base (Decreased electron desnity at Natom)

However, acetamide can be regarded as a resonance hybrid of the contributing forms (I and l
the
where + R-effect of amino group decreases the electron density at the nitrogen atom. Due to this
is much less available to capture the proton. Hence, it is weaker
lone pair of electrons on nitrogen a

base than ethylamine.

7. Effect on dipole moment: It is well known that the overall dipole moment of a molecule
the
of all the polar bonds. However, resonance may increase or decrease
is the resultant of dipole moments
the nature of the polar bonds present in
the magnitude of this resultant dipole moment depending upon
the molecule. Following examples are illustrative:
of vinyl chloride (1.45 D) is much lower
(a) Lowering of dipole moment: The dipole moment
in vinyl chloride, the
than that of ethyl chloride (2.05 D). This is due to the reason that
its
-I-effect and +R-effect of chlorine operate in opposite directions thereby decreasing
of chlorine operates.
dipole moment as compared to that of ethyl chloride where only-I-effect

(H 2.05 D)- 1-effect only

CH-CH, Cl
Ethyl chloride

Ch,CHC- :CH-CH=Q
Vinyl chloride
(H = 145 D)

+R-effect, direction of dipole moment

CH=CH CI
- I-effect, direction of dipole moment
T

of chlorobenzene (1.69 D) is
In a similar manner, explained why the dipole
it can be moment

lower than that of ethyl chloride (2.05 D).

D) is higher than
(b) Increasing the dipole moment: The dipole moment of p-nitroaniline (4.92
+R-effect
In p-nitroaniline, the -I-effect of nitro group and
that of nitrobenzene (4.22 D).
the observed higher
reinforce each other (act in the same direction). Hence,
of amino group
as compared to nitrobenzene.
dipole moment of p-nitroaniline
 ORGANIC CHEMISTRY VOL

52
NO -

1-effect of NO2P group

m o m e n t

ection of dipole
due to NO group -OO
N

HN H,N-K
O

Direction of dipole moment due -I-effect

to
Direction of dipole moment due to +-effect of NH; The large iodida
The iodide
iodide:

picryl
in g r o u p which
Difference in C-N bond length for o
8. p-nitro
and
groups

p-nitro
effect o n
has no ro group
p-nitro
atom forces o-nitro groups out of the ring and involving
plane of benzene
benzene ring
remains in the plane of the ring. Therefore, resonance in
i
only. As a result, carbon-nitrogen bond acauires some double bona c
operates

* *
pm.
1s
hence, ine C-N bond length 'a' is longer (145 nm) than 'b' which ou

a NO
O,N NO 0,N

b N
N
8

Picryl iodide