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AROMATIC ELECTROPHILIC
SUBSTITUTION REACTIONS
CECH-202
UNIT-3(A)
By - Ms MAYURI R SOMPURA
INTRODUCTION
By - Ms MAYURI R SOMPURA
reactions
Non-polar
(free radical)
addition substitution
polar
electrophilic nucleophilic
SOURCE OF ELECTRONS – BENZENE
By - Ms MAYURI R SOMPURA
• Every carbon atom of benzene is 𝑠𝑝2 hybridized.
• Each carbon posses a set of three 𝑠𝑝2 hybrid orbitals.
• They are used to form two sigma bonds with neighboring carbons
and one to form sigma bond with hydrogen.
• Every carbon has one unhybridised 2𝑝𝑧 orbital occupying one
electron.
• This orbital is perpendicular to the plane of benzene ring.
SOURCE OF ELECTRONS – BENZENE
By - Ms MAYURI R SOMPURA
• All these six orbitals overlap with each other to form a new molecular
orbital.
• These molecular orbitals are not fixed to one carbon atom.
• They keep on circulating in the molecular orbital and are responsible
for formation of additional 𝜋 bond between carbon atoms.
• Hence, they are known as delocalized 𝜋 electrons.
• These are also responsible for aromaticity of benzene.
SOURCE OF ELECTRONS – BENZENE
By - Ms MAYURI R SOMPURA
• By presence of 6 𝜋 electrons:-
Benzene behaves as lewis base
Source of electrons to attract electrophile
Undergoes SE (substituted electrophilic) reactions
MONO - SUBSTITUTION IN BENZENE
By - Ms MAYURI R SOMPURA
DEFINITION OF SE REACTIONS
By - Ms MAYURI R SOMPURA
• The replacement of an atom or a group attached to carbon of benzene
nucleus, by another group is known as aromatic substitution.
• If the incoming group is an electrophile, then it is known as electrophilic
aromatic substitution reaction.
MONO - SUBSTITUTION IN BENZENE
By - Ms MAYURI R SOMPURA
• All six hydrogens of benzene are identical, hence when one H atom is
replaced only one product is obtained.
MONO - SUBSTITUTION IN BENZENE
By - Ms MAYURI R SOMPURA
GENERAL MECHANISM OF SE REACTION
By - Ms MAYURI R SOMPURA
• Suppose reagent is EZ.
• This furnishes electrophile E+ and remaining part Z- acts as nucleophile.
• Mechanism has two steps:-
1. Attack by E+ upon benzene to form stable benzenonium ion
(carbocation type)
2. Abstraction of H+ from benzenonium by Z- to from product Ph-E.
GENERAL MECHANISM OF SE REACTION
By - Ms MAYURI R SOMPURA
1. Generalization of necessary electrophile.
GENERAL MECHANISM OF SE REACTION
By - Ms MAYURI R SOMPURA
2. Attack from electrophile onto benzene.
• This is a slow step reaction.
• Hence, rate determining step.
GENERAL MECHANISM OF SE REACTION
By - Ms MAYURI R SOMPURA
3. Resonance :- positive charge is dispersed all over the ring which results
into a stable speices.
GENERAL MECHANISM OF SE REACTION
By - Ms MAYURI R SOMPURA
4. Abstraction of H+:
• This is a fast reaction & it gives final product.
ENERGY PROFILE GRAPH
By - Ms MAYURI R SOMPURA
EVIDENCE
By - Ms MAYURI R SOMPURA
• Kinetics :-
➢Rate determining step involves two molecules – benzene and reagent; so it
is an bimolecular electrophilic substitution reaction.
• Spectroscopy :-
➢The existence of E+, Z- & benzonium ion has been proved by
spectroscopy.
➢( nuclear magnetic resonance spectroscopy and infra red spectro)
ASSIGNMENT
By - Ms MAYURI R SOMPURA
What is an electrophile ?
What is a nucleophile ?
What is electromeric effect ?
How will you define substitution reactions ?
Define – electrophilic substitution reactions
How can we consider benzene as a source of electrons ?
What is the general mechanism of SE reactions ?
Give mono substituted reactions of benzene.
Draw energy profile graph discussing general electrophilic substitution reactions

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Aromatic electrophilic substitution reactions

  • 2. INTRODUCTION By - Ms MAYURI R SOMPURA reactions Non-polar (free radical) addition substitution polar electrophilic nucleophilic
  • 3. SOURCE OF ELECTRONS – BENZENE By - Ms MAYURI R SOMPURA • Every carbon atom of benzene is 𝑠𝑝2 hybridized. • Each carbon posses a set of three 𝑠𝑝2 hybrid orbitals. • They are used to form two sigma bonds with neighboring carbons and one to form sigma bond with hydrogen. • Every carbon has one unhybridised 2𝑝𝑧 orbital occupying one electron. • This orbital is perpendicular to the plane of benzene ring.
  • 4. SOURCE OF ELECTRONS – BENZENE By - Ms MAYURI R SOMPURA • All these six orbitals overlap with each other to form a new molecular orbital. • These molecular orbitals are not fixed to one carbon atom. • They keep on circulating in the molecular orbital and are responsible for formation of additional 𝜋 bond between carbon atoms. • Hence, they are known as delocalized 𝜋 electrons. • These are also responsible for aromaticity of benzene.
  • 5. SOURCE OF ELECTRONS – BENZENE By - Ms MAYURI R SOMPURA • By presence of 6 𝜋 electrons:- Benzene behaves as lewis base Source of electrons to attract electrophile Undergoes SE (substituted electrophilic) reactions
  • 6. MONO - SUBSTITUTION IN BENZENE By - Ms MAYURI R SOMPURA
  • 7. DEFINITION OF SE REACTIONS By - Ms MAYURI R SOMPURA • The replacement of an atom or a group attached to carbon of benzene nucleus, by another group is known as aromatic substitution. • If the incoming group is an electrophile, then it is known as electrophilic aromatic substitution reaction.
  • 8. MONO - SUBSTITUTION IN BENZENE By - Ms MAYURI R SOMPURA • All six hydrogens of benzene are identical, hence when one H atom is replaced only one product is obtained.
  • 9. MONO - SUBSTITUTION IN BENZENE By - Ms MAYURI R SOMPURA
  • 10. GENERAL MECHANISM OF SE REACTION By - Ms MAYURI R SOMPURA • Suppose reagent is EZ. • This furnishes electrophile E+ and remaining part Z- acts as nucleophile. • Mechanism has two steps:- 1. Attack by E+ upon benzene to form stable benzenonium ion (carbocation type) 2. Abstraction of H+ from benzenonium by Z- to from product Ph-E.
  • 11. GENERAL MECHANISM OF SE REACTION By - Ms MAYURI R SOMPURA 1. Generalization of necessary electrophile.
  • 12. GENERAL MECHANISM OF SE REACTION By - Ms MAYURI R SOMPURA 2. Attack from electrophile onto benzene. • This is a slow step reaction. • Hence, rate determining step.
  • 13. GENERAL MECHANISM OF SE REACTION By - Ms MAYURI R SOMPURA 3. Resonance :- positive charge is dispersed all over the ring which results into a stable speices.
  • 14. GENERAL MECHANISM OF SE REACTION By - Ms MAYURI R SOMPURA 4. Abstraction of H+: • This is a fast reaction & it gives final product.
  • 15. ENERGY PROFILE GRAPH By - Ms MAYURI R SOMPURA
  • 16. EVIDENCE By - Ms MAYURI R SOMPURA • Kinetics :- ➢Rate determining step involves two molecules – benzene and reagent; so it is an bimolecular electrophilic substitution reaction. • Spectroscopy :- ➢The existence of E+, Z- & benzonium ion has been proved by spectroscopy. ➢( nuclear magnetic resonance spectroscopy and infra red spectro)
  • 17. ASSIGNMENT By - Ms MAYURI R SOMPURA What is an electrophile ? What is a nucleophile ? What is electromeric effect ? How will you define substitution reactions ? Define – electrophilic substitution reactions How can we consider benzene as a source of electrons ? What is the general mechanism of SE reactions ? Give mono substituted reactions of benzene. Draw energy profile graph discussing general electrophilic substitution reactions