Organische Chemie 3

Les 1
Delocalized electrons

TCHY-OC36V-14
Teacher: Anika Jonker
anika.jonker@hu.nl
Welcome!

n Course:
n 12 lessons (Monday & Wednesday)
n IZT: self-study time: 90 min
n Theoretical exam of 150 min (in English)

n Material:
n Bruice Organic Chemistry 7th edition (Rob Niekel: Bruice & Wade)
n Powerpoints on Sharepoint

n Questions? Come and see me; or mail: anika.jonker@hu.nl

(not on Thursday :P)
Overview of the families in Organic Chemistry

Organic Chemistry 3
Organic Chemistry 1 & 2

Organic Chemistry 2
Benzene

Benzene is cyclic, planar, and has an interrupted cloud of π electrons.

Benzene is an unusually stable compound.

Resonance

The delocalization energy is the extra stability a compound has

as a result of having delocalized electrons.

Electron delocalization is also called resonance.

Delocalization energy is also called resonance energy.

The resonance hybrid is more stable than any of its

resonance contributors is predicted to be.
Resonance energy

Little delocalization energy

Significant delocalization energy

Advantage of resonance

The delocalization energy of benzene is 36 kcal/mol.

Benzene is an aromatic compound
Criteria for aromaticity

• It must have an uninterrupted cloud of π electrons.

(cyclic, planar, every ring atom must have a p orbital).

• The π cloud must have an odd number of pairs of π electrons.

Hückel’s rule

Aromatic compound: 4n + 2 = number of π electrons

Aromatic compound has odd number of pair π electrons

Cyclobutadiene has an even number of pairs of π electrons.

Cyclooctatetraene has an even number of pairs of π electrons and

it is not planar.
Charged cyclic compounds
8/21
Aromatic heterocyclic compounds
9/21
Pyridine & Pyrrole

The aromatic ring of pyridine is less electron dense than benzene

because the nitrogen withdraws electrons from the ring.

The aromatic ring of pyrrole is more electron dense than benzene

because the nitrogen donates electrons into the ring.
Stability
Nomenclature: monosubstituted benzene

Some monosubstituted benzenes are named

just by adding the name of the substituent to
“benzene”
 Nomenclature: common names
13/21

De naam en Some monosubstituted benzenes have names

structuren van de that incorporate the substituent
verbindingen met
een sterretje moet je
kennen.
Important difference: phenyl & benzyl
14/21
Alkyl substituted benzenes
15/21

• Name as alkyl-substituted benzenes when the alkyl group has a

• name.
Name as phenyl-substituted alkanes otherwise.
• Toluene (methyl substituent on benzene) is an exception.
How benzene reacts
16/21

Aromatic compounds such as benzene undergo

electrophilic aromatic substitution reactions.
Electrophilic aromatic substitution - mechanism

Aromaticity is restored in the product from electrophilic substitution.

Reaction coordinate diagram
General mechanism electrophilic aromatic substitution

Examples:

• Halogenation (Br, Cl, I)

• Nitration (NO2)
• Sulfonation (SO3H)
• Friedel-Crafts acylation (RC=O)
• Friedel-Crafts alkylation (R)