Presented by:-
Dr. Santosh Singh
Assistant Professor
D.D.U. Govt. P.G. College, Saidabad,
Prayagraj
Reaction mechanism
Electronic displacement
Electronic displacementin Electronic
Fission displacement
of bonds Naturedisplacement
Electronic of attacking
covalent
in bond
covalent bond in covalent bond in covalentreagent
bond
Inductive effect
Mesomeric effect or Homolytic Heterolytic Electrophile Nucleophile
resonance effect
Electronic effect All positively charged species having vacant
Hyperconjugation p-orbital
Anomeric effect All neutral molecule having incomplete octet
All neutral molecule having vacant d-orbital
Electronic displacement in covalent bond:- For any reaction, the electronic displacement must occurs in the
covalent bond of substrate. These are following effects which are responsible for electronic displacement of covalent bond.
Inductive effect
Mesomeric effect or Resonance
Electromeric effect
Hyperconjugation
Anomeric effect
Due to electronic displacement in covalent bond, same electron deficient and same electron
rich centre arises in the molecule thus the molecule become polar and reactive
ii)
( Mesomeric effect)
electron displace due to
conjugation Electron deficient Electron rich
iii)
Displacement of electron due to presence of attacking reagent
iv)
(Hyperconjugation)
Displacement of electron with electron
v)
(Anomeric Effect)
Inductive Effect
Inductive Effect : Polarity produce in a molecule due to displacement of electron toward the more
electronegative atom is known as Inductive Effect . For eg.
I -Effect I -Effect
Displacement of electron away from a group Displacement of sigma electrons towards a group
or atom are called +I –Effect. For eg :
or atom are called - I –Effect.
All alkyl group behaves as +I group.
All positively charged group behaves as -I
group For eg :
All electronegative atoms behave as -I group.
Exception case organo-metallic compound alkyl For e.g:
group behaves as - I –Effect . For eg : -R-Mg-X F, Cl, Br, I, –NO2, –CN,-SH, SR, -+CH2 etc
Acidic strength:-
When G is +I group
Basicity +I effect
Conjugation arises in a molecule due to interaction between two molecular orbital in which one
molecular orbital is filled whereas other molecular orbital is vacant.
For conjugation, each atom must be present on sp2 hybridization and shape should be planar.
Types of conjugation
1- b - *
b *
b *
b *
2- n- *
* n
Note:-
In conjugation or mesomeric effect only - electrons & lone pair electron present in p- orbital participate.
Hybrid orbital does not participate in conjugation.
For conjugation molecular orbital or atomic orbital must be present in same plane.
3. b- vacant p orbital interaction:-
Polarity produced in a molecule due to displacement of π-electrons in a conjugated molecules. For eg.
-M effect
+M effect
Displacement of π electrons away from a Displacement of π electrons towards a
group or atom in conjugated molecules is group or atom in conjugated molecules is
known as +M- effect. known as –M - effect.
+M group are those group which contain at -M effect group are those group which
least one high energy filled orbital contain low energy vacant d or π* orbital.
(lone pair)
e.g.
-OH , -NH2 ,-OCH3, -SH , -SCH3 , -F , -Cl , -
Br , -I etc.
All +M group are ortho & para directing group All –M group behaves as meta directing group
All +M group also shows –I effect All +M group also shows –I effect.
-M effect order:
The interaction of sigma bonding molecular orbital with either vacant * or vacant p orbital or vacant
* orbital or with vacant d orbital or p orbital having single electron are known as hyperconjugation.
For eg:
b * b p b
b p *
b - * b - p b - p b - *
b – p b - * b - * b - *
Application of Hyperconjugation
Stability of alkene :
Stability of alkene No of hyperconjugative structure
Stability of Carbocation:
The interaction b/w non-bonding M.O. with vacant s* M.O. is known as anomeric effect
Resonance effect: -
If there are several structures require for explanation of a molecule or to define the property of the molecule
then we say that the molecule shows resonance & these structures are called resonating structure. Resonance
either arises due to localisation of π-electrons or σ electrons. All mesomeric effect, hyperconjugation,
anomeric effect is also resonance effect.
If a molecule shows resonance then resonance hybrid is the structure which completely define the molecule.
In Resonance hybrid, all resonating structures contribute. The extent of contribution is directly proportional
to stability of resonating structure.
Stability of Resonating structure
Neutral resonating structure are more stable than charged resonating structure
Or
Resonating structure having more covalent bond are more stable
Or
Resonating structure in which each atom present with complete octet is more stable
For eg.
A is more stable than B and C because A is neutral, contains more covalent bond and have
complete octet.
In case of charged resonating structure, resonance structure having minimum opposite charge
separation and maximum same charge separation is more stable.
B is more stable than C
Resonating structure in which negative charge present on electronegative atom and positively
charge present on electropositive atom are more stable. For eg.
O2 O 2- O 2+ O22-
𝑩𝒐𝒏𝒅 𝒔𝒕𝒓𝒆𝒏𝒈𝒕𝒉
𝑩𝒐𝒏𝒅 𝒐𝒓𝒅𝒆𝒓 𝜶
𝑩𝒐𝒏𝒅 𝒍𝒆𝒏𝒈𝒕𝒉
Polyatomic molecule: -