General organic chemistry

Inductive effect/ Transmission effect

Induction of polarity in the non-polar bond due to presence of a polar bond is
known as inductive effect.
E

Es

is
Eg:- CH3—CH2—Cl
Is a permanent effect
r

Is weak and poor effect

r

Distance dependent effect i.e (Acc. To above example)

Es
is
r

Effects only in Sigma bond crowding

a

Invalid in - bond crowding

E
4
 TYPES
+I effect/+group -I effect/+Igroup

e- donating group
rn

e- withdrawing grouop
Has tendency to increase e-

MT
Decreases e- density in the C-chain
density in the C-chain attached
attached with it.
with it.

Eg:- CH3—CH2—O Eg:- CH3—CH2—OR2

:
:
 CH3 CH3

CH2 > NH > O > COO > —C—CH3 —CH3 > CH > CH2–CH3 >

CH3 CH3

CD3 > CH3 > D > H

CH2 , न ह , ओ , carboxylate , 3 > 2> 1 >CD3 > CH3

-I effect :- Shown by all neutral except saturated alkyles.

HYDROGEN Taken as reference

Inductive effect considered to be zero
 O
—OR2 > —NF3 > NR3 > NH3 > NO2 > SO3H > CN > —C—R

> —F > —Cl > Br > I > OR > OH > C—CH > NH2 > Ph > CH = CH2 > H
-

ओ र 2 >, ना फरहान >, ना िरित क >, ना हीरा लाल >, ना ओमपुरी >,
SO3H >, Cyanide >, Acid >, Father >, Collector >, Beta >, Inspector >, Aur >,

OH >, Alkyne >, Amine >, Benz , ene

Resonance

Conjugation:- If in a molecule /ion , a orbital can overlap with more than one
p-orbital, conjugation is said to be there.

€7
Eg:-

:
Conditions for a compound to have conjugation :->
P-orbitals must be present at adjacent atoms.
P-orbitals must be parallel.
Units having conjugation

1.) Conjugation
¥

2.) (+ve charge ) or - vacant orbital conjugation

±

3.) (-ve charge)

E-

Sp2 hybridised with 2 electrons

f
 4.) Lone pair conjugation
É

5.) Umpaired e- conjugation

É

I Sp2 hybridised + p-orbital having 1

electron

6.) Lone pair - vacant orbital conjugation

:

CH3—O—CH2—CH3
:
In which of the following compounds conjugation is absent ??
=

ñ
N

::
>

I
i

S
✗
 I
ñ

>
✗
I

at
O
CH3—C—O
 • •
•
•
E
E
E E
 •
E
•
E
E E
 T
E
E
E E
 É
E
O
CH3—C
O
g-

In this , N-don’t have vacant p-orbital

E
en
En
 Delocalisation
Take place in a conjugated system.
r

Increases stability of conjugated system.

r

÷
"
If a molecule / ion can’t be represented by single
r

Resonance
structure ,then 2 or more hypothetical structures are
used to represent .
These structures are called resonating structure/ Canonical structures.
.
Rules to write valid resonating structures:-

(1) Relative position of atoms must be same .

i.e Sigma bond must not be broken .

(2) No. of unpaired electrons must remain same.

(3) 2nd period elements must not have more than 8electrons in their outermost
shell.

Actual structure of a conjugated system and its

Resonance hybrid:-
contribution of all valid resonating structures.

Contribution Stability of resonating structures

r
Relative stability of different resonating structures:-
Resonating structure having more no. of atoms with complete octet will be
T

more stable.
Eg:- (1) CH3—CH—CH=CH—O—CH3

(2) CH3—CH=CH—CH=O—CH3

Stability 2>1
More no. of covalent bonds = more no. of atoms whose octet is complete

Bonds will always be same.

:
Non-polar resonating structures will be more stable than resonating structures.
9

O O

CH3—C—OH CH3—C—OH
1>2
 Resonating structures having -ve charge present at more electronegative atom
r

will be more stable.

O O

CH2=C—H CH2—C—H
1>2
Resonating structure having +ve charge present at most electropositive atom
r

will be more stable.

Resonating structure having opposite charge close to each other will be

r

more stable.

Resonating structure having like charges close to each other will be less
r

stable.
 Compare stability:-
(A) O
O
(1) CH3—C=O—H (2) CH3—C—OH

O O
(3) CH3—C—OH (4) CH3—C—OH
 Solution:- 4>1>3>2

(B)
(2)
(1)

(3)
 Solution :- 3 > 1 > 2

(C)
(1) (2)

(3)

Solution :- 2 > 3 > 1

Resonance energy:- Defined as the difference between energy of most
stable resonating structure and that of resonance
hybrid.
Draw resonating structures:-

CH2 CH CH CH CH2
-
n

CH2 CH CH CH CH2

CH2 CH CH CH CH2
→

Es
CH2 CH Is
CH CH CH2

i
÷

:
÷
 CH2 CH CH CH CH2
>
it

CH2 CH CH CH CH2

is

÷
Csi
CH2 CH CH CH CH2 CH2 CH CH CH CH2

÷
÷
CH2 CH CH CH O CH3
:
>

:
it

CH2 CH CH CH O CH3

CH2 CH CH CH O CH3
is

do

Es
]

CH2 CH CH CH O CH3
:
÷
i

'
÷
÷
 is
⇐ . -
-
is
t
i
r
r
s it
Mesomeric effect:-
Permanent polarity induced/ produced in a conjugated system due to
n

delocalization of p-electrons.
Will be a permanent effect.
^^

Strong effect. (Only effects ortho and para positions, meta-unaffected)

Distance independent effect.
9

Two types
+M -M
Increases e- density in attached Decreases e- density in attached
C-chain C-chain

If lone pair is attached on 1st atom —> +M effect

99

If lone pair is absent and atom is attached to most electronegative atom by

multiple bond —> -M effect
Check +M or -M effect :-

(1) NH2 +M

O
(2) —C—CH3 -M

(3) —O—Eth
+M

(4) CN
-M
(5) CH=NH -M

(6) NO2

Me

(7) N
Ethyl

(8) NO2

(9) —CH2
(10) COOH

(11) —O

0
(12) —C—O—Me

(13) —NH

O
(14) —NH—C—Me
 O
(15) —C—NH—Eth

(16) F

(17) NO

(18) —Ph

(19) —CH=CH2
(20) CH3

(21) CH2—OH

APPLICATIONS OF RESONANCE
Complete conjugation (if all atoms are involved in conjugation)
No Yes
÷
Non-aromatic compound Count e- involved

⇐
[4n+2] e- [4n] e-

⇐
n=0,1,2,3…… n=0,1,2,3,4
Satisfy Haeckal ‘s rule Anti-aromatic
Aromatic
Stability :- Aromatic > Non - Aromatic > Anti- Aromatic

= —> 1
—> 1

÷
- —> 1
+/ v.o —> 0

Identify the following ; whether Aromatic, Non- Aromatic and

Anti- Aromatic:-
(1) (2) (3)

N A AA
(4) (5) (6)

as

A N

(Because vacant p-orbital)

(7)
(8) (9)
(10) (11) (12)

-m
(13) (14) (15)

-
•
•
(16) (17) (18)

•
•
••
:

(19) (20) (21)

:
(22) (23) (24)

(25) (26)
(27)

_m
 Quasi-Aromatic
Structure in which we have to draw resonating structure to check if it is
Aromatic , Non-Aromatic or Anti-Aromatic.

(1)

(2)
(3)

(4)

(5)
(6)

(7)

Bond length:-
"
A > B>A—B>A—B
A—B>A B>A B
÷
÷
Compare C — C bond length:-
(A) (1)
(2)

(3)
 Solution : 1>2>3
(B) (1)
(2)

(3)
Solution :- 3>2>1
(C) (1)
(2)

(3) (4)
Solution : 2 > 3 > 4 > 1
(D) (1)
(2)

(3)
: (4)
Solution : 2 > 4 > 3 > 1

# While comparing bond length within a molecule , check by

resonating structures.

(1)
a

→
O
CH3 C

b O
←
Solution:-
O

CH3 C
O

R.S 1 R.S 2 Bond length

a 2 1 1.5

b 1 2 1.5
(2)

X
O
CH3 C
OH
Y
solution:- O

CH3 C
OH
Stability R.S 1 > 2

R.S 1 R.S 2 So, X > 1.5

Y < 1.5
X 2
1

Y 1 2
Hyperconjugation Effect:-
Nathen and Baker effect / No - Bond Resonance
Here, ⇐
bond overlaps with Sigma bond.
^^

Delocalization of and electrons.

⇐
b
Permanent effect.
^^

Stronger than inductive but weaker than mesomeric.

- hydrogen must be present for hyperconjugation and p-orbital must not be

8

completely filled.
geo
ji
-
⑤

C C
→

— carbon —> Sp3 hybridised

s
 Units which can show hyperconjugation :-

⑦
(1)
C C
⑦

•
(2) C C
⑤

(3) C C C

C- anion can’t participate in hyperconjugation.

In hyperconjugation , when C-H bond is involved , it will be an e- donating
a

effect. Hence called +H effect.

Calculate total no. of Hydrogen which are involved in

i
hyperconjugation:-

(1)

(2)
•
Solution:- 1.) 4 H

88
2.) 3 H

(3)

(4)
Solution :- 3.) 8 H

88
4.) 6 H

(5)
•

(6)
Solution :- 5.) 6 H 6.) 3 H

r
r
If hyperconjugation , effect of a group attached with Benzene ring increases
e- density at ortho & para positions & meta position remain unaffected.
Applications of Hyperconjugation effect

(1) Heat of hydrogenation / Heat of hydrogenation of Alkene

H2/Pt
C C C C + Heat
(Always exothermic)

HOH No. of double bonds/ pie bonds

88

HOH 1
Stability

If bond is involved in resonance , then stability will be more.

 Compare HOH
#

(A) (1)
(2)

(3)
Solution :- 2 > 1 > 3
(B) (1)
(2)

(3)
Solution :- 3>2>1
(C) (1)
(2)

(3) (4)
Solution :- 1>4>3>2
(D)(1)
(2)

(3)

(5)
(4)
Solution :- 2>4>5>3>1

Electronic effect
Complete transfer of electrons towards one of the two atoms on demand
n

E
of external attacking reagent.
Temporary effect
ra

Strong effect

Case 1
H
C C C C

H
Case 2 CN
C O C O

CN
 Two types

it
f.
.

+E effect

If attacking reagent and electrons

-E effect

On different atom.

r
are on same atom.
Eg:- Case 1 Eg:- Case 2

^
.

In which of the following Electronic effect is possible:-

(1) (2)
(3) (4)

E
(5)
 Solution :- On all except 3rd.
For electronic effect to take place , presence of - bonds is

K
must.

Homolytic

Bond breaking / Bond fission

Heterolytic

§
Homolytic A + B

:
A — B

A B A—B

:
Free radicals are formed.
~
 Factors favouring :- High temperature.
r

Non- polar solvent.

Presence of free - radical attacking reagent.
Presence of peroxides.
Presence of light.

Heteroytic:-
:
A—B —> A + B
Leads to formation of cation and anion.
Factors favouring :- Low temperature
Presence of polar solvents.
Presence of ion attacking reagents.
Reaction intermediate

R —> P
Single step reaction

R —> A —> B —> C —> P

A & B short lived,unstable, reactive
Multistep reaction
quantity formed during reaction

Reaction intermediates

No. of intermediates :- n-1 ( n = no. of steps)

 Minima represents Intermediate
¥÷ whereas maxima represents no.
of steps.