General Organic Chemistry-I 1

Making & Breaking Of Bonds

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General Organic Chemistry-I 1
Making & Breaking Of Bonds
Hyperconjugation

It is delocalisation of sigma electron with p-orbital.

Hyperconjugation

(i) Hyperconjugation in Alkenes

Hyperconjugation

(ii) Hyperconjugation in Carbocation

Hyperconjugation

(ii) Hyperconjugation in Radical

Hyperconjugation

(iv) Hyperconjugation in Toluene

Applications

(a) Stability of Alkenes

More is the number of hyperconjugative structures more stable

is the alkene.
“More alkylated alkenes are more stable”.
Stability of alkenes ∝ delocalisation of π electrons ∝ no. of
hyperconjugative structures.
Applications

(b) Heat of hydrogenation

Greater the number of 𝛂 hydrogen result greater stability of

alkene.
Thus greater extent of hyperconjugation results lower value of
heat of hydrogenation.
Applications

(c) Bond Length

Bond length is also affected by hyperconjugation.

(i) Bond length of C(II) – C(III) bond is less than normal C – C

bond.
(ii) Bond length of C(II) – C(I) bond is more than normal C = C
bond.
(iii) C – H bond is longer than normal C – H bond.
Applications

(d) Stability of reaction intermediates

(i) Stability of carbocation ∝ +M, +H, +I groups.

(ii) Stability of carbon free radical ∝ + I groups.
(iii) Stability of carbanion ∝ – M, – I groups.
Reaction Mechanism

Bond Fission

Breaking of a covalent bond is called bond fission.

They are of 2 types.

HOMOLYTIC FISSION (HOMOLYSIS)

(i) Breaking of a covalent bond in such a way that both the

atoms or species retain one electron each.
Reaction Mechanism

Bond Fission

Breaking of a covalent bond is called bond fission.

They are of 2 types.

HOMOLYTIC FISSION (HOMOLYSIS)

(ii) Fission takes place in a symmetrical manner

U.V.light
A | A A + A
U.V.light
eg : CH3 CH3 CH3 + CH3
|

Methyl free radicals

Reaction Mechanism

Bond Fission

Breaking of a covalent bond is called bond fission.

They are of 2 types.

HOMOLYTIC FISSION (HOMOLYSIS)

(iii) It results in formation of free radicals,

Short lived, unstable and highly reactive species.

(iv) Takes place in the presence of UV light,

hightemp,peroxide or sunlight.
Reaction Mechanism

Bond Fission

HETEROLYTIC FISSION (HETEROLYSIS)

i) Breaking of a covalent bond in such a way that one of the

atom or species retains a Pair of electrons.

ii) Fission takes place in unsymmetrical manner

A+ + B–
Polar
A B
|

Solvent
A– + B+

⇒ Depending upon electronegativity

Reaction Mechanism

Bond Fission

HETEROLYTIC FISSION (HETEROLYSIS)

iii) It results in formation of ions. (i.e., cations and anions)

Reaction Mechanism

Homolytic Fission Heterolytic Fission

In this case, the In this case, the

covalent bond breaks covalent bond breaks
symmetrically. unsymmetrically.
Reaction Mechanism

Homolytic Fission Heterolytic Fission

Each species obtains The more

and retains one electronegative atom
electron from shared retains the shared
electron pair electron pair
Reaction Mechanism

Homolytic Fission Heterolytic Fission

Electrically neutral Electrically charged

free radicals are ions
formed which carry (cations and anions)
an odd electron. are formed.
Reaction Mechanism

Homolytic Fission Heterolytic Fission

It takes place in It takes place in the

the presence of presence of polar
sunlight, U.V. light. solvent.
Identify correct C – O bond length order

A. i > ii > iii

B. ii > iii > i
C. i > iii > ii
D. iii > i > ii
The resonance energy of each of the following is

A. i > ii > iii

B. ii > iii > i
C. i > iii > ii
D. iii > i > ii
Identify order of per ring resonance energies of each of the
following

A. i > ii > iii

B. ii > iii > i
C. i > iii > ii
D. iii > i > ii
REAGENTS
Electrophilic Reagents

⮚ These are electron loving species.

⮚ These are electron deficient species.

⮚ They attack the site of high electron density in the substrate.

⮚ They may be + vely charged ions (cations) or neutral molecules

⮚ They possess an atom with incomplete octet.

Electrophilic Reagents

⮚ They are Lewis acids.

⮚ They accept an electron pair from the substrate to form a

covalent bond.
+ +
e.g.: H , NO2 , BF3 , AlCl3, etc.
Nucleophilic Reagents

⮚ These are nucleus loving species.

⮚ These are electron rich species.

⮚ They attack the site of low electron density in the

substrate.
⮚ They may be negatively charged ions (anions) or neutral
molecules.

⮚ They possess an atom with lone pair of electrons.

Nucleophilic Reagents

⮚ They are Lewis bases.

⮚ They donate an electron pair to substrate and forms a co-

ordinate covalent bond(dative bond).

.. ..
e.g.: OH— , CN— , H – .O. – H , NH3 , etc.
REACTION INTERMEDIATES
Carbonium Ion (Carbocation)

+
⮚ Carbon atom is positively charged C

⮚ Electron deficient species

⮚ Carbon atom possesses six electrons in its outermost shell.

⮚ sp2 hybridisation.
⮚ Its shape is triangular planar.
Carbonium Ion (Carbocation)

Stability of carbonium ion :

+
(CH3)3 C > (CH3)2C H > CH3CH2 > CH3 C
tert Sec pri. methyl

⮚ It can accept an electron pair from a nucleophile to form a

covalent bond.
⮚ It is a Lewis acid
e.g.: tert-butyl carbocation (CH3)3 C+
Carbonium Ion (Carbocation)

General stability of order of carbocation

+
+ + + + +
Classification of Carbocation

Alkyl Carbocations are classified into three categories i.e.,

primary (1°), Secondary (2°) and tertiary (3°).
Structure of Carbocation

• A carbocation (also called a carbonium ion or a carbenium

ion) is a positively charged carbon.
• Carbon is sp2 hybridized with vacant p orbital.
Alkyl Carbocations
Inductive Effect
The relative stability of the following carbocations is

A. i > ii > iii

B. ii > iii > i
C. i > iii > ii
D. iii > i > ii
The relative yield of the following products from the reaction of
HCl with 1-methyl-1,3-cyclohexadiene at 50°C is

A. i > ii > iii

B. ii > iii > i
C. i > iii > ii
D. iii > i > ii
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