Organic Chemistry

GOC

OM PANDEY
JRF : AIR 13
M.S. : IIT DELHI
B.S. : Gold Medalist
In the following sets of resonating structure, label the major and minor
contributors towards resonance hybrid.
 ••
(P) CH3 — CH — C  N ↔ CH3 — CH

••
C N
  
(Q) CH3 — CH — CH CH — NO2 ↔ CH3 — CH CH — CH N—O
  
O
(R) CH3 — CH2 — C — NH2 ↔ CH3 — CH2 — C NH2

NH2 NH2

O O O O

(S) CH3 — C — CH — C — CH3 ↔ CH3 — C CH — C — CH3
Write the stability order of following resonating structures :

O
In which of the following pairs A is more stable than B? JEE (Main) 2014

(A) (B)

(C) (D) Ph3C•, (CH3)C•

Which one of the following substituents at para-position is most effective
in stabilizing the phenoxide ion? JEE (Main) 2014

(A) – CH3 (B) – OCH3 (C) – COCH3 (D) – CH2OH

Which of the following compounds is not aromatic? JEE (Main) 2019

(A) (B) (C) (D)

Which compound(s) out of the following is/are not aromatic? JEE (Main) 2019

(A) (B) (C) (D)

Which of the following compounds will produce a precipitate with AgNO3 ?
JEE (Main) 2019

(A) (B) (C) (D)

Which of the following has the shortest C–Cl bond? JEE (Main) 2020
(A) Cl – CH CH – NO2
(B) Cl – CH CH – CH3
(C) Cl – CH CH2
(D) Cl – CH CH – OCH3
 Cleavage Of Bond

Homolytic Cleavage Heterolytic Cleavage

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

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.

 Types of Inductive Effect
+ I Effect – I Effect
More electropositive than hydrogen. More electronegative than hydrogen.

It donates electron pair towards It withdraw sigma electron pair from

carbon chain carbon chain.
 + I Effect – I Effect

(i) Anion (i) Cation

(ii) Metals (ii) Halogens

(iii) Alkyl groups (iii) Groups of E.N. atoms

 Predict the character of groups / atoms, regarding Inductive Effect ?
O O
|| ||
(i) —C — OH (vi) —O — C — R

O O
|| ||
(ii) —C — ONa (vii) —C — NH2

O
|| −
(iii) —C — O — CH3 (viii) — CH
2

(xi) — ONa
+
(iv) —C  N (ix) — CH2

(v) —N O (x) —O—H

 Order of + I & – I
+ I order
Anions

Alkyl Groups

+ I order
- I order

Halogens (i) – F – Cl – Br –I

F
(ii) – CH — CH2 — F
F

F Cl
(iii) — C —C
— —
F Cl
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
|| ||
—C — H —C — Cl

O O
|| ||
—C — H —C — R
 – I order
More substituted heteroatom is more E.N. than less substituted

(i) —O —O
H R

(ii) — NH2 — NHR — NR2

(iii) — S — H —S—R

(iv) — SH2 — SR2

(v) — NH3 — NR3

 – I order

— NR3 — SR2 — NH3 — NO2 —CN

—F — Cl — Br —I —O—R —O—H

—CC—R — CH = CH2

E.N. spc spN3

Resonance
 Resonance
Delocalisation of pi electron in conjugated system
 Conjugation
Necessary condition for resonance

Types of conjugation

(i)  -  Conjugation (ii) Z

Radical Z

Lone Pair Z

Cation Z

Anion Z
 Rules for writing Resonating structures

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

NH

(ii) Sigma skeleton should not be changed.

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

H
C
H
 H
N
H

N
—

O
C
H
 Some Other Conjugation Types

H H
•• ••
C C Z C C N—H
H H

H –
C C Z CH2 C C CH2
H

H + H +
C C Z C C C H
H H
 Rules for stability of resonating structures
R.S. having more no. of  bonds, with complete octet, is more stable.

NH2 — BH2

NH2 — CH2

If  bonds are same, then less ionized R.S. is more stable.

NH2
Cl
 Rules for stability of resonating structures
If  bonds are same and –ve charge is present at

Same Period Elements C N O

O
||
CH3 — C — NH

O
||
CH3 — C — CH2

Different Period Elements O N

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

O O

N O N O
O O

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.

(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
|| ||
(a) O CH3 — C — O CH3 — S — O
||
O

(b) NH2 H3CO

(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
 Predict order of stability ?

O O O
O
(iii)
(i) C C
NH2 NH NH NH

NH2 NH2
(ii) (iv) CH2

NH2 OH
CH2
 Mesomeric Effect

Flow of electron

NH

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

If group has x, y relation.

 + M Order

(i) — CH2 — NH —O (vi)

— NH2
(ii) — OH — NH2

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

(iv) — OH — O — CH3 CH3

—N
CH3
(v) — SH — S — 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
N
NH2
C

There is no effect, at meta position.

 Select the position for maximum electron density.

O—H
(iii)
(i)

N O
O

O
||
NH — C — CH3
G
(ii) (iv)
 Hyper-Conjugation

H2C — H

Condition
 Hyper-Conjugation

Delocalisation of  electron with (a) p orbital

(b) * orbital

Carbocation
Radical H
H
C—C
H H
H
Alkene H H
C—C
H CH2
H
 Benzene H

H C H

There is no effect, at meta position.

Find no. of  hydrogen present in following molecule ?

H CH3
(i) C C (iv)
H CH3

H3C CH3
(v)
(ii) C C
CH3 CH3

(vi)
(iii) CH
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
 Negative Hyper Conjugation
F
F

—
F —C—F
(i) H2C — C — F (iii)
F

F
—

(ii) C— F
F
 Order of Effectiveness

CH2

CH2

CH2
 Electron density in benzene ring

Electron donating tendency +M +HC +I

O O
|| ||
NH2 NH — C — CH3 O — C — CH3

CH3 Cl
—

—
C — CH3 C — Cl
CH3 Cl
 Electron density in benzene ring

H H

—
C —H C — CH3
H H

H CH3
—

—
C — CH3 C — CH3
CH3 CH3
 Electron density in benzene ring

H2C — H D2C — D

O
||
CH3 CH2 — CH3 Cl C—H
 Electron density in benzene ring
N
O
||
C C—H Br
 Bond length

H H
(i) C C C C
H H

(ii)
 Bond length

(iii)

(iv)
(v)
 Heat of Hydrogenation  Hhyd

H H
C C
H H
 Factors affecting heat of hydrogenation
No. of  bond

CH2 = CH2

CH  CH

Reactivity :

P.E. :
Stability of Alkene

CH3 CH3 H2/Pd

C C
CH3 CH3

H H H2/Pd
C C
CH3 CH3
Find order of Hhyd ?

(i)

(ii)

(iii) HC  C — C  CH CH2 = CH — CH = CH2

(iv)
Resonance Energy [Hhyd]exp [Hhyd]cal

+ H2 Pt – 120 kJ / mol

+ H2 Pt – 232 kJ / mol

+ H2 Pt – 208 kJ / mol

Difference between amount of experimental & Calculated Hhyd .

Find order of resonance energy ?

(i)

O NH
|| ||
(ii) CH3 — C — CH2 CH3 — C — CH2

(iii) O CH2 HN CH2 CH2

(iv)

(v) CH2
 Aromaticity
Aromatic Compounds

(i) Cyclic

(ii) Planar

(iii) Conjugation

(iv) Huckle Rule

 Aromaticity
Aromatic Compounds Antiaromatic Compounds

(i) Cyclic (i) Cyclic

(ii) Planar (ii) Planar

(iii) Conjugation
(iii) Conjugation
 Stability of Compounds

P.E.
Benzanoid System
 Cations

+ +
(i) (v)

+
(ii)
+ (vi)
+N
+
H
(iii)

+ (vii)
+N
(iv)
H H
 Cations

+
(viii)
O

+
(ix)
N

H
+
(x)
 Anions
–
(i) (iv)
–

–
(ii)
–
(iv)
–
–

(iii)
 Heterocyclic Compounds

(i) B—H (iv)

O

O
(ii) (v)
S

(iii) (vi)
N N
H
 Relative Aromatic Character

Benzene Thiophene Pyrrole Furan

S N O

Order of E.N. :

Electron donating tendency :

in resonance
 Aromaticity

COT

[COT]2+

[COT]2–
 O

(4)
(1)

(5)
(2)

(3) (6)
 (1) (2) (3)

Order of B.L. :
Order of D.M. :

Order of Aromaticity :

Order of Stability :
Order of R.E. :

Order of Rotational Energy :

Annulenes Monocyclic ring with alternate double — Single bond.

x X  – CH2 / – NH / – O / – S
 Azulene

Isomer of Napthalene Dark blue colour

𝜇 = 1.08 D

Negative charge is present in 5 ring

& positive charge in 7 membered ring.
 Which of the following can give AgBr on reaction with AgNO3 ?
Br Br Br
Br
(i) (ii) (iii) (iv)
Br
Find the order of dipole moment? O
O
O O
(i) (ii)
Which of following can evolve H2 gas after reaction with Na metal ?

H H

H H