GENERAL ORGANIC

SIMPLY CONCISE
CHEMISTRY
GENERAL ORGANIC CHEMISTRY
Reagent
Substrate [Intermediate] Product + byproducts
C⁺, C⁻, C˙

Fission of a Covalent Bond: Attacking Reagents:

C A
SIMPLY CONCISE
1) heterolytic cleavage -
+
C + A
-
1) Nucleophiles - nucleus loving
have a pair of e⁻ to donate
eg - CH₃⁻, X⁻, RO⁻, H₂O, NH₃
carbocation

2) Electrophiles - electron loving

- +
C A C + A
have empty orbitals to receive e⁻
carbanion
eg - >C=O, SO₂, CH₃, X, NO₂
2) homolytic cleavage -
Electron displacement effects:
C A
.
C + A
. 1) Inductive 2) Mesomeric

carbon free radicle

3) Hyperconjugation
 INDUCTIVE EFFECT
polarisation of σ-bond caused by the polarisation of adjacent σ-bond

-I Effect: due to EWG +I Effect: due to EDG

I effect is negligible
δδδ+ δδ+ δ+ δ- δδδ- δδ- δ- δ+ after the 3rd C atom
CH₃ CH₂ CH₂ Cl CH₃ CH₂ CH₂ NH⁻

-I Effect order:
+ + SIMPLY CONCISE
+
-NF₃ > -NR₃ > -NH₃ > -NO₂ > -SO₃H > -CN > -CHO > -COOH > -F > -Cl > -Br > -I > -OR > -OH>
≡
-C CH > -NH₂ > -Ar > -C=CH₂ > -H

+I Effect order:
- - - -
-CH₂ > -NH > -O > -COO > 3°R > 2°R > 1°R > -H
 INDUCTIVE EFFECT
Applications of Inductive effect
- + .
1) To compare stability of C , C and C
+ + - - . .
C C C C C C

∝ ∝ ∝
SIMPLY CONCISE
stability +I & 1/-I stability -I & 1/+I stability +I & 1/-I

effect of distance > number > power

2) To compare acidic strength of aliphatic alcohols & carboxylic acids

O O
- + - +
C O H C O + H O H O + H
stronger acid more stable stronger more
acid stable

acidic
strength
∝ -I & 1/+I
 INDUCTIVE EFFECT
Q. Compare acidic strength

F -I Cl Cl -I
effect of distance > number > power
OH < OH

OH -I SIMPLY CONCISE +I

COOH > COOH

acidic
strength
∝ -I & 1/+I
 HYPERCONJUGATION
delocalisation of e⁻ from filled BMO to adjacent empty orbital
+ .
requirement: α-H at sp³ C wrt C=C / C / C // no. of HCS = no. of α- H

alkenes: σ - π*
+

SIMPLY CONCISE
H H H H
- + - -
H C CH CH₂ H C CH CH₂ H C CH CH₂ H C CH CH₂
+
H H H H

carbocation: σ - p
+
H H H H
+ +
H C CH₂ H C CH₂ H C CH₂ H C CH₂
+
H H H H
 HYPERCONJUGATION
delocalisation of e⁻ from filled BMO to adjacent empty orbital
+ .
requirement: α-H at sp³ C wrt C=C / C / C // no. of HCS = no. of α- H

free radical: : σ - p
.

SIMPLY CONCISE
H H H H
. .
H C CH₂ H C CH₂ H C CH₂ H C CH₂
.
H H H H

negative conjugation:
-
Cl Cl Cl Cl
+ - + +
Cl C CH CH₂ Cl C CH CH₂ Cl C CH CH₂ Cl C CH CH₂
-
Cl Cl Cl Cl
 HYPERCONJUGATION
Applications of hyperconjugation
+ .
1) To compare stability of alkenes, C and C
stability ∝ no. of HCS = no. of α- H
effect of HC > I effect

SIMPLY CONCISE
2) To compare heat of hydrogenation of alkenes

C C + H₂ CH CH

HoH ∝ 1/stability ∝ 1/no. of α- H

Q. Compare stability

3 3 3 3

+ > + 2
3
2
3
2 -I
3
3
> 3
NH₂

3
 RESONANCE
delocalisation of πe⁻ & lp e⁻ of the molecule
+ δ+
+ δ+
O O O

..

..

..
O

..
..

..

..

..
+ δ+
resonating structures resonance hybrid
Note:
SIMPLY CONCISE
resonance increases stability of the molecule
stability of RH > stability of RSs
contribution of RS ∝ stability of RS
Condition:
molecule should be planar - sp²
σ
conjugation should be there - charge charge
- - + -
A B C A B C A B C D A B C D
+ +
A B C A B C
 RESONANCE
Stability of resonating structures:
1) neutral RS is more stable than charged RS
+ -
Cl CH CH₂ > Cl CH CH₂

2) stability ∝ no. of π bonds

S I M P L Y C O N C I S E
+ -
H₂C CH CH O > H₂C CH CH O

3) stability ∝ stability of charges

+ - - +
H₂C CH CH O > H₂C CH CH O

4) stability ∝ 1/opp. charge seperation

- -
O O
+ <
+

5) stability ∝ like charge seperation

+ -
.. > ..
- OCH₃ + OCH₃
 MESOMERIC EFFECT
change in e⁻ distribution in a molecule due to resonance

+M Effect: due to EDG -M Effect: due to EWG

.. - + + -
H₂C CH OH .. H₂C CH OH H₂C CH C O H₂C CH C O
.. .. .. .. ..

SIMPLY CONCISE
-OH, -OR, -NH-CO-R, -O-CO-OR, -NH₂ -NO₂, -CN, -SO₃H, -CHO, -CO, -COOR,
.. .. ..
.. ..
-Ph, -X -COOH, -CO-NH₂, -NO
.. , -NO, -R
.

order of M effect:
O cross conjugation
.. .. .. ..
H₂C CH OH
.. < H₂C CH NH₂ H₂C CH OH
.. > H₂C CH O
.. C CH₃

Note:
1) while comparing : M > HC > I 2) M effect doesn‘t operate at meta position
exception - halogens : -I > +M ..
OH CHO
-I : F > Cl > Br > I
+M : F > Cl > Br > I
⇒ F < Cl < Br < I δ- δ- δ+ δ+
withdrawing
nature δ- δ+
 MESOMERIC EFFECT
Applications of mesomeric effect
1) To compare acidic strength of aromatic alcohols & carboxylic acids
O O
- -
C O H C O O H O

SIMPLY CONCISE H
+ acidic
strength
∝ -M & 1/+M H
+

stronger acid more stable stronger acid more stable

Note -
1) Ortho effect in benzoic acids - 2) effect of H bonding -
O
COO
- OH
- G ≠ H, F, OH, CN ...
C O NO₂
OH
G
more acidic less acidic

due to Steric Inhibition of Resonance,

acidic strength increases
 ACIDIC STRENGTH
Q. Compare acidic strength:

COOH COOH COOH COOH COOH COOH

NO₂

> > -I < <

SIMPLY CONCISE
NO₂
-I, -M
ortho ortho ortho ortho
NO₂

COOH COOH OH OH

> > >

CH₃ OCH₃ NO₂ CH₃

acidic
strength
∝ -M & 1/+M
+M ↓ +M -M +M
 BASIC STRENGTH
Basic strength of nitrogenous bases:
H ..
H₂C CH NH₂
N
..
+ H
+
N
+ basic
strength
∝ +M, +I & 1/-M, -I delocalised lone pair - less basic

Ortho effect in aromatic amines:

..
N
G
SIMPLY CONCISE
G ≠ H, F, OH, CN ...

due to Steric Inhibition of Resonance (SIR),

basic strength of 2° & 3° aromatic amines increases

+
NH₂ G ≠ H, F, OH, CN ...
G

due to Steric Inhibition in Protonation (SIP),

basic strength of 1° aromatic amines decreases
 BASIC STRENGTH
Q. Compare basic strength:
.. .. ..
N N N - -
SIR

>
> > +I

SIMPLY CONCISE
+I, +M

.. .. .. - > -
NH₂ NH₂ NH₂
SIP

< +I <
+I, +M
 AROMATICITY
Huckle’s Rule for Aromaticity:
1) Aromatic - ring + planar + cont. conjugation + (4n+2)πe⁻
2) Anti aromatic - ring + planar + cont. conjugation + (4n)πe⁻
3) Non aromatic - if any of the first three condition is not true

SIMPLY CONCISE tub like

structure
[4]-annulene [6]-annulene [8]-annulene
anti aromatic aromatic non aromatic
+ +
+ Stability : A > NA > AA
Effect : Aro > M > HC > I

aromatic anti aromatic aromatic

 AROMATICITY
Questions on Aromaticity:
1) Compare the dipole moment
-O -O
-O
+ +
+ aro anti aro dp : c > a > b

SIMPLY CONCISE
a) b) c) more
resonance

2) Compare rate of dehydration

OH 2 OH 2
OH 2
+ + rod : c > a > b
+ aro anti aro
a) b) c) more
resonance
 CARBOCATIONS
Stability:
1) BB > Aro > M > HC > I Back bonding
2) stability ∝  +M, +I, +HC + .. +
∝ 1
H C
H
OH H C
H
OH

-M, -I, -HC

SIMPLY CONCISE
3) hybridisation : sp³ > sp² > sp

Q. Compare stability:
+
3

+ > + > 2 + + + > +

3 3 3 3 + < <
sp sp² sp³

+ + +M, -I +
OCH₃
+ +
> > -I < .. < ..
+M, -I
OCH₃
↓ OCH₃ +
OH
BB
OH
BB
NH₂
 CARBOCATIONS
Rearrangement in carbocation:
1) Shift - increases stability

2 1,2 - hydride 2 2 1,2 - methyl 2

shift shift
+ + + +

SIMPLY CONCISE
1 1 1 1
H

2) Ring Expansion - reduces strain & increase stability

+ 1
+
2 1 +
2
2 1

Q. Which of the following will not rearrange:

+
H +
+ H + + +
+
 CARBANIONS
Stability:
1) BB > Aro > M > I Back bonding
2) stability ∝  -M, -I - -
∝ 1 H C
H
Cl H C
H
Cl

+M, +I

SIMPLY CONCISE
3) hybridisation : sp³ < sp² < sp

Q. Compare stability:
- - -
- < - < - - -
- > >
+I +I +I sp sp² sp³ > >
-M +M
NO₂ OCH₃
 FREE RADICALS
Stability:
1) M > HC > I
2) stability ∝  +M, +I, +HC
∝ 1
-M, -I, -HC

SIMPLY CONCISE
3) hybridisation : sp³ > sp² > sp