Inductive Effect

Chemistry
Session
GENERAL ORGANIC CHEMISTRY - 4

Session Objectives
Session Objectives
1. Resonance or Mesomeric effect

2. Inductive effect
3. Electromeric effect
4. Hydrogen bond
5. Hyper conjugation
6. Steric effect
Resonance or Mesomerism
1. All the properties of a compound
cannot be explained by single
structure.
2. Canonical structures or resonance
contributing structuresdiffer in position
of electrons.
3. Delocalisation of electrons leads to decrease in
potential energy of molecule.
canonical structures of Resonance hybrid

benezene structure of benezene
Resonance or Mesomerism
4. Resonance hybrid is more stable than

canonical structures.
5. Resonance structures are imaginary.
6. Resonance energy = Actual energy of hybridenergy of

most stable contributing structure.
7. Resonance is measure of stability.

Rules for Drawing Resonance Structure
1. The molecule should be planar.

2. It contains an alternating system
of single and double bonds
(a conjugated system).
3. The relative positions of nuclei should remain unchanged
(e.g. tautomerism).
4. The negative charge must preferably lie on the most
electronegative atom.
5. The charge needs to be preserved in all the resonating
structures.
6. The electrons always move away from a negative charge.
7. Arrows should be drawn to indicate the direction of the
movement of electrons.
Types of Resonance
+R or +M effect
+
C C OH CC OH
(+M or +R effect of OH group)
R or M effect
+
C C CH O CC CH O
(R effect of CHO group)

Types of Resonance
For substituted benzene
+ +
NH2 NH2 NH2

etc.

+R effect of NH2 group.

O O O O O O
+ + +
N N N
+
etc.
+
R effect of NO2 group.
Inductive Effect
1. Permanent effect in saturated
carbon chain compounds.
2. Group attached to carbon chain should
have tendency to release or withdraw
electrons.
Types of inductive effect
+ I effect effect electron donating groups

e.g., CH3 , C2H5
I effect effect electron withdrawing groups

e.g., - NO2 , CN
Features of Inductive Effect
1. Chloroacetic acid is a stronger acid
than acetic acid because
O O
Cl - CH2 C Cl-CH2 - C +
+ H
OH -I O
Ka = 1.4 10-3
O O
+
CH3-C CH3-C + H
OH +I O
Ka = 1.75 10-5
2. The larger is the electron-withdrawing

effect of a group, the greater is the
I (inductive) effect.
F CH2 COOH Br CH2 COOH
Ka 2.510-3 1.310-3
3. Inductive effect is additive
Cl3CCOOH Cl2CHCOOH
Ka 2.310-1 5.410-2
4. Since this effect is transmitted

through a chain it becomes less
effective with distance
ClCH2CH2COOH ClCH2CH2CH2COOH
Ka 8.3210-4 3.0210-5
Electromeric Effect
Temporary effect which is observed

in presence of reagents involving
transfer of electrons in an unsaturated
system.
in presence
of reagent +
X Y X Y
in absence
of reagent
Electromeric Effect
Addition of HBr to an alkene
R 2 R
1 H H
HBr
C C CC
H H + H
H
R
+ +
Br H
R CH CH3 C CH3
H
Br
Hyperconjugation or no bond
resonance
(a) Involves and bond orbitals

(b) More the number of hyperconjugative
structures, more will be the stability of
ion or molecule
+ H H
H H H H H
+
H C C+ HC=CH H C=C HC=C
+
H H H H H H H H
Structure of ethyl carbonium ion

Hyperconjugation or no bond
resonance
(c) The number of hyperconjugative
structures in an alkene is obtained by the
number of C H bonds attached to the
carbon bonded directly to the double
bonded carbon atoms.
H H+ H
+
H C CH CH2 H C CH CH2 H C CH CH2
H H H
H

H C CH CH2
H
+
Significance of Hyperconjugation
H3C CH CH CH2 H3C CH CH CH2

+
H
1butene (2 hyperconjugative structures)

H3C CH CH CH3 H3C CH CH CH2
+
H
(6 hyperconjugative structures)
2butene
More stable
Relative strength of organic acids
O O
R-C O
R-C + +
H R-C
OH O O
Resonance structures
Class Exercise
Class exercise 1
The hybridization of carbon
atoms C C single bond in
vinylacetylene is
(a) sp3 - sp3 (b) sp - sp2
(c) sp2 - sp (d) sp3 - sp
Solution :
1 2 3 4
H2C CH C CH Hence answer is (c).
Vinylacetylene
Class exercise 2
Allyl isocyanide has
(a) 9 bonds and 4 bonds
(b) 8 bonds and 5 bonds
(c) 8 bonds, 5 bonds and 4 non-bonding electrons
(d) 9 bonds, 2 bonds and 2 non-bonding electrons
Solution: +
H2C CH CH2 N C
Allyl isocyanide
The compound has 3 bonds and

one lone pair, i.e. two non-bonding
electrons. It also contains 9 -
bonds. Hence answer is (d).
Class exercise 3
Among the following which has the
most acidic -hydrogen?
O O O
(a) CH3CCH2CHO (b) CH3CCH2CCH3
(c) CH CCH COOCH (d) CH3CHO

3 2 3
Solution
O O

H3C C CH2 CH one keto and one
aldehydic carbonyl group.
O O

H3C C CH2 C CH3 two e-withdrawing keto
groups.
O O

H3C C CH2 C OCH3 keto and ester group.
O

H3C CH one aldehyde group.
Solution
Since e-withdrawing nature of C O
gas varies as aldehyde > keto > ester
Then most acidic a-H atom is present in

O O
H3C C CH2 CH
Hence answer is (a).

Class exercise 4
The decreasing order of acidity among
phenol, p-methylphenol, m-nitrophenol
and p-nitrophenol is
(a) m-nitrophenol, p-nitrophenol, phenol,
p-methylphenol
(b) p-nitrophenol, m-nitrophenol, phenol,
p-methylphenol
(c) p-methylphenol, phenol, m-nitrophenol,
p-nitrophenol
(d) phenol, p-methyl phenol, p-nitrophenol,
m-nitrophenol
Solution
OH OH OH OH
NO2
CH3 NO2
+I I I, R
Electron withdrawing groups increase acidic strength

while electron donating group decreases the same.
So the proper decreasing order of acidic strength is
OH OH OH OH
> > >

NO2 Hence answer is (b).
NO2 CH3
Class exercise 5
In the following compounds, the order
of basicity is
O
N N N
N
H H H
(I) (II) (III) (IV)
(a) I > IV > II > I (b) II > I > IV > III

(c) III > I > IV > II (d) IV > I > III > II
Solution
N N N N
sp3 sp2 sp3
H sp2
H H
I II IV III
Between I and IV, IV is less basic because of the I

effect of oxygen atom.
II is more basic than III as the lone pair on N-atom in
III is not available for protonation as it is involved in
resonance.
Therefore, the correct order is I > IV > II > III
Hence answer is (a).

Class exercise 6
Account for the order acidity in the
following compounds.
O
(i) CH3CCH2COOH CH3CH2COOH
(ii) HC CCH2COOH H2C = CHCH2COOH

Solution
O

(i) H3C C CH2 COOH > CH3 CH2 COOH
(a) (b)
In compound (a), electron-withdrawing keto group increases

the acidic strength by decreasing the O H bond strength,
while no such effect is there in compound (b).
(ii) HC C CH2 COOH > CH2 CH CH2 COOH
Carbon atoms attached to triple bond is sp hybridised and

more electron-withdrawing than sp2 hybridised carbon atom.
Hence, such order in acidic strength is observed.
Class exercise 7
Which of the following two amines is

more basic and why?
CCl3CH2CH2CH2NH2 or CCl3CH2CH2NH2
Solution
Electron-withdrawing groups decrease
the charge density on N-atom of
organic amines and hence decrease the
basic strength. In Cl3C CH2 CH2 CH2
NH2, the electron withdrawing CCl3 is
far apart from NH2 group as
compared to Cl3C CH2 CH2 NH2.
Hence, the former is more basic in
nature.
Class exercise 8
Do you think CH3CH CH2
OH
can show tautomerism?
Solution:
Yes. The tautomeric form is CH3COCH3.

Class exercise 9
Which one will be more acidic ?
OH OH
CH3 CH3 CH3 CH3

NO2 C
N
I II
Solution
Because of steric inhibition of

resonance conjugate base of I will not
be stabilised by resonance. But for II
there is no such steric inhibition of
resonance.
Class exercise 10
Which hydrogen is maximum
acidic in the following compound?
HC C NO2
OH
COOH
Solution:
Carboxylic hydrogen is maximum acidic.

Thank you

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Chemistry

GENERAL ORGANIC CHEMISTRY - 4

1. Resonance or Mesomeric effect

canonical structures of Resonance hybrid

4. Resonance hybrid is more stable than

5. Resonance structures are imaginary.

6. Resonance energy = Actual energy of hybridenergy of

7. Resonance is measure of stability.

1. The molecule should be planar.

(+M or +R effect of OH group)

(R effect of CHO group)

Types of inductive effect

+ I effect effect electron donating groups

I effect effect electron withdrawing groups

2. The larger is the electron-withdrawing

3. Inductive effect is additive

4. Since this effect is transmitted

Temporary effect which is observed

Addition of HBr to an alkene

(a) Involves and bond orbitals

Structure of ethyl carbonium ion

H3C CH CH CH2 H3C CH CH CH2

(c) sp2 - sp (d) sp3 - sp

The compound has 3 bonds and

(a) CH3CCH2CHO (b) CH3CCH2CCH3

(c) CH CCH COOCH (d) CH3CHO

Since e-withdrawing nature of C O

gas varies as aldehyde > keto > ester

Then most acidic a-H atom is present in

Hence answer is (a).

Electron withdrawing groups increase acidic strength

> > >

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

Between I and IV, IV is less basic because of the I

Hence answer is (a).

(ii) HC CCH2COOH H2C = CHCH2COOH

In compound (a), electron-withdrawing keto group increases

(ii) HC C CH2 COOH > CH2 CH CH2 COOH

Carbon atoms attached to triple bond is sp hybridised and

Which of the following two amines is

Do you think CH3CH CH2

can show tautomerism?

Yes. The tautomeric form is CH3COCH3.

CH3 CH3 CH3 CH3

Because of steric inhibition of

Carboxylic hydrogen is maximum acidic.

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