❑ Subject – Organic Chemistry

❑ Chapter - GOC

ONE SHOT Om Pandey, IIT Delhi

1 Inductive Effect

2 Resonance & Mesomeric Effect

3 Hyperconjugation , Aromaticity

4 Acidic Nature & Basic Nature

4 Tautomerism
 Cleavage Of Bond

Homolytic Cleavage Heterolytic Cleavage

Inductive Effect The effect which includes push or pull of electrons in
covalent  bonds.

Properties
It generates partial (+) and (–) charge in organic compound.

It is a permanent effect.

It is a distance dependent effect.

It operates only through  bonds.

 + I Effect Types of Inductive Effect – I Effect

More electronegative than hydrogen.

More electropositive than hydrogen.
It withdraw sigma electron pair from
It pushes electron pair towards carbon chain. carbon chain.

Anion Cation

Metals Halogens

Alkyl groups Groups of E.N. atoms

+ I order Anions

Alkyl Groups

- I order (i) — F — Cl — Br —I

E.N. spC sp3N F

(ii) — CH — CH2 — F
F

F Cl
—C Cl
—
(iii) —C F
—

F Cl
– I order Different Hybridisation : — C  C — H — CH CH2 — CH3

—CN — C NH — CH2 — NH2

Different F.G. : — OH — NH2

O O O O
|| || || ||
—C — H —C —Cl —C — H —C — R

More substituted heteroatom is more E.N. than less substituted

(i) — O —O
H R

(ii) — NH2 — NHR — NR2

H3C — CH3 : 154 pm
— CH2 : 134 pm
H2C —
Experimental data for Benzene C — C : 139 pm

Resonance Delocalisation of pi electrons

Orbital Representation of Resonance
Conjugation Necessary condition for resonance

Types of conjugation (i)  -  Conjugation

(ii) Z

Lone Pair NH2

+
Cation CH2

-
Anion NH

Radical
.
CH2
Rules for writing Resonating structure

(i) Follow octet rule for 2nd period element.

(ii) Sigma skeleton should not be changed.

(iii) The no. of paired / unpaired electrons should be same.

O
C
H

O-
 Rules for stability of resonating structures
a) Resonating Structure having more no. of  bonds, with complete octet, is more stable.

+ +
NH2 — CH2 O CH3

b) If  bonds are same, then less ionized Resonating Structure is move stable.

NH2
Cl
c) If  bonds are same and –ve charge is present at Same Period Elements
Then –ve charge is more stable at more electronegative atom.

O
|| - -
CH3 —C —CH2 O CH2

d) If  bonds are same and –ve charge is present at Different Period Elements
Then –ve charge is more stable at larger size atom.

O
||
CH3 —C —S
-
e) If  bonds are same, then aromatic resonating structures is more stable.

O -

N O
O

f) In fused benzene ring system, structure with more no. of kakule benzene will be
more stable.
 Stability of Resonating structures of different molecules
(i) Larger conjugation is more stable than smaller conjugation.

- -
CH2 CH2

(ii) Linear conjugated system is more stable than cross conjugation.

(iii) If nature of bonding is different then (–)ve charge is more stable at more
electronegative atom and (+)ve charge is more stable at less electronegative atom.

O- O O
|| ||
O- CH3 —C —O - CH3 —S —O-
||
O

+ +
NH2 HO
(iv) – ve charge is more stable at larger size element.

O O O
C C C
-S S- -O S- -O O-

(v) Benzenoid system having more no. of kakule benzene is more stable.
Bredt’s Rule Bridgehead atom can not be planar

H H

H
 Mesomeric Effect
Flow of electron

-NH

+
CH2
 Types of Mesomeric Effect
+ M Groups – M Groups
If first atom of the group has –ve charge If first atom of the group has vacant orbital
or lone pair

If group has x, y relation .

 + M Order
- -
(i) — CH2 — NH — O- (vi)

— NH2
(ii) — OH — NH2

H
O O —N
|| || CH3
(iii) —O—C —CH3 —NH —C —CH3

CH3
—N
(iv) — OH — O — CH3 CH3
 + M Order

- - -
— CH2 — NH —O — NH2 — NHR — NR2

O O
|| ||
— OH — OR —NH —C — R —O—C — R

—F — Cl — Br —I
 - M Order
O O
|| || O O O
(i) —C — NH2 —C —OH || || ||
(ii) —C —OH —C —O—C — R

O O
|| ||
(iii) —C —OH —C —OR

O O
|| ||
(iv) —C — H —C —CH3

(v) — NO2 —C N
– M Order
O O
|| ||
— NO2 —C N —C — H —C —CH3

O O O O O
|| || || || ||
—C —O—C — R —C —OR —C —OH —C — NH2

—C —O —C — NH —C —CH2
|| || ||
O O O
 + M and – M Effect on Benzene
+ M Groups – M Groups
H
NH2 C

There is no effect, at meta position.

 Select the position for maximum electron density.

O—H
(iii)
(i)
O N O

O
||
NH —C —CH3
G
(ii) (iv)
 Hyper Conjugation
De-localisation of  electron with (a) p orbital

(b) * orbital
Carbocation

H
+ H
C—C
H
H H
 H
. H
Radical C—C
H
H H

H H
C—C
Alkene H CH2
H

H
Benzene H C H
Find no. of  hydrogen present in following molecule for hyperconjugation ?

H CH3 H3C CH3

(i) C C (ii) C C
H CH3 CH3 CH3

Stability of Alkene
NOTE : Hyper conjugation generates double bond character in single bond and
single bond character in double bond.
H CH3
H C H H3C — C — CH3
 Order of Effectiveness

Resonance +
CH2

Hyperconjugation +
CH2

Inductive Effect +
CH2
 Electron density in benzene ring
Electron donating groups Electron withdrawing groups
+M , +HC , + I -M -I

O
||
C—H Br OH
CH3
 H
Bond length (i) C C C C
H

(ii)

(iii)
Heat of Hydrogenation  Hhyd

H2/Pd
CH2 = CH2

H2/Pd
CH  CH

No. of  bond :
Potential Energy :
 Stability of Alkene

CH3 CH3
H2/Pd
C C
CH3 CH3

H H H2/Pd
C C
CH3 CH3
 Aromaticity
Aromatic Compounds

(i) Cyclic

(ii) Planar

(iii) Conjugation

(iv) Huckle Rule

Antiaromatic Compounds Non-aromatic Compounds
(i) Cyclic

(ii) Planar

(iii) Conjugation
(iv) 4 n  electrons

P.E.
 Benzenoid System

–
–
Anions (iii)
(i)

–
(ii) (iv)
– –
 Cations
+
+ +
(vi)
(i) (iii) O

(ii)
(iv)
+N
H

(v)
+N
H H
 Heterocyclic Compounds

(i) (iv)
N N

(ii)
O

(iii)
S
 Aromaticity

COT

[COT]2+

[COT]2–
 O
(iv)
(i)

(ii)
 Reaction Intermediates
Carbocation Carbanion Free Radical

- .
C
+ C C

Nature :

Hybridisation :

Stability :
 + + +
Stability of Carbocation (a) CH3 CH3 — CH2 CH3 —C —CH3
|
CH3

+ + + + +
CH2 CH2 CH2 CH2 CH2

(b)

CN Cl OCH3
CPM [ Cyclopropylmethyl carbocation]
Rearrangement of Carbocation
H
| +
CH3 —CH —CH2

Ring Expansion Ring Contraction

+
CH2 +

+
CH2
Stability of - - -
(i) CH3 CH2 — CH3 CH2 — CH — CH3
Carbanion
Cl
- - -
(ii) CH2 — CH3 CH2 — CH2 — Cl CH2 — C — Cl
Cl
F Cl
(iii) - C — F - C — Cl
F Cl
- CH2 - CH2 - CH2 - CH2

(vi)

N Cl OCH3
O
Stability of Radical

. . .
CH3 —C CH3 — CH C
| |
CH3 CH3

.
CH2
.

. .
O CH2 CH2
 Basicity and Acidity
Arrhenius Theory
H+ Donor : Acid
H+ Acceptor : Base

Bronsted and Lowry Theory

H+ Donor : Acid
H+ Acceptor : Base

Lewis Theory

Lone Pair Donor : Base

Lone Pair Acceptor : Acid
 Basicity and Kb

Kb Electron donating Tendency

Kb Bond Strength b/w H and Basic atom

 Factors Affecting Basicity

Electronegativity – CH
3
– NH
2
– OH –F

Size OH– –F

SH– – Cl

– Br

–I

Hybridisation : Same basic atom with different hybridisation

NH2 NH NH2 N
Aniline - Electronic Effects
NH2 NH2 NH2

CH3 NO2

NH2 NH2
Aniline and Amines
Aniline / Pyridine & Pyrrole NH2

N N

NH2
Aniline and Amides
Solvation Applied in saturated Aliphatic Amines
NH3 RNH2 R2NH R3N

R = CH3

R = C2H5
Solvation Applied in ortho substituted Aniline / Pyridine

NH2

NH2
G
 Solvation

Kb :
N N N

NH2 NH2 NH2

Kb :
 Delocalisation of +ve charge in C.A.

Amidines →

Guanidine →
 Acid

HF

HI
 Factors affecting acidic strength

Electronegativity H2O HF

Size H2O HF

H2S
HCl

HBr

HI
 Carboxylic Acid
O
||
CH3 —C —O— H

O
O O Cl ||
|| ||
CH —C —O— H
CH3 —C —O— H Cl —CH2 —C —OH
Cl
 Benzoic Acids
O O O
|| || ||
C —OH C —OH
C —OH

CH3 NO2
 Phenols

OH OH
OH

CH3 NO2
Hydrogen Bonding If H-bonding is present in acid ⟹ Ka

H
OH O O OH OH
N
O
NO2
NO2
Alcohol Phenol Carbonic acid Carboxylic Acid Sulphonic acid
Ortho Effect Applied for ortho substituted Benzoic Acid

O O O O
|| || || ||
C —OH C —OH C —OH C —OH
G

G
G
If all B.A.’s are ortho – substituted then Ka is decided by SIR effect.
O O O O
|| || || ||
C —OH C —OH C —OH C —OH
CH3 C2H5

O O O
|| || ||
C —OH C —OH C —OH
HO OH OH

OH
 Tautomerism
H
|
—C — X = Y
|

Conditions (i) Acidic / Basic medium

(ii) sp3 carbon with at least 1 hydrogen attached to –M group
It involves change in the position of  Bond and hydrogen atom.
 Enolisable Hydrogen
O
||
CH3 —C —CH3

O
H H

H H
 O
||
CH3 —CH = CH —C —CH3

O O
Question Which of the following will not show Tautomerism ?

O O
D
A

O—H
|
C H
O
E
C
CH3
 % Enol Content
O

H H

Stability of Enol
(1) Aromaticity (3) Hydrogen Bonding

(2) Hyper-Conjugation (4) Resonance

 % Enol Content

Hydrogen Bonding

1, 3 diketone

1, 2 diketone
O O

O
O
 % Enol Content

O
H O O CH3 ||
| || || —C — H
CH2 —C — H CH3 —CH —C — H
| H2C
H |
H