AROMATIC

COM P O U N DS ( 1 )

 Aromaticity
 The H u c kl e’s R u l e
e te ro c yc l es
 Aromatic H
 Aromaticity…

Cyclohexene reacts rapidly with Br2 and gives

Benzene is much less reactive than the addition product 1,2-dibromocyclohexane

typical alkene and fails to undergo

the usual alkene reactions
Benzene reacts only slowly with Br2 and gives
the substitution product C6H5 Br
 Aromaticity…

Benzene and Benzene is cyclic and conjugated

other
Benzene is unusually stable, it is 150 kJ/mol (36 kcal/mol) more stable than might be
benzene-like expected

aromatic
Benzene undergoes substitution reactions that retain the cyclic conjugation rather than electrophilic

molecules addition reactions that would destroy the conjugation

share similar
Benzene is a resonance hybrid whose structure is intermediate between two line-bond
characteristics structure
 The Hückle’s Rule…

A molecule is aromatic
only if it has a planar,
monocyclic system of
conjugation and contains
a total of 4n + 2 p
electrons
- Erich Hückel (1931)-
 The Hückle’s Rule…

A molecule is aromatic only if it has a planar, monocyclic system of conjugation

and contains a total of 4n + 2 p electrons, where n is an integer (n = 0, 1, 2, 3,…)

The
Hücke Only molecules with 2, 6, 10, 14, 18,… p electrons can be
aromatic

l’s rule Molecules with 4n p electrons (4, 8, 12, 16,…) can not be aromatic, said to be antiaromatic
because delocalization of their p electrons would lead to their destablization
 The Hückle’s Rule…

Examples of Contains six p electrons (4n + 2 = 6 when n = 1)

the Hückel’s
rule is Benzene It’s Aromatic
 The Hückle’s Rule…
• Benzene’s Orbital Energy

p6* _____

p4* _____ _____ p5*

E
p2 _____ _____ p3

p1 _____
 The Hückle’s Rule…

Contains four p electrons wich are localized into two double bonds
Examples of rather than delocalized around the ring

the Hückel’s
rule is Antiaromatic, highly reactive, shows none of the properties
Cyclobutadien associated with aromaticity

e
 The Hückle’s Rule…
• Cyclobutadiena’s Orbital Energy

p4* _____

E p2 _____ _____ p3

p1 _____
 The Hückle’s Rule…

Contains eight p electrons which are localized onto four double bonds rather than delocalized around the ring

Examples of
the Hückel’s
Not aromatic
rule is
Cyclooctatetra The molecule is tub-shaped rather than planar
ene
 The Hückle’s Rule…
• Cyclooctatetraene’s Orbital Energy
p8* _____

p6* _____ _____ p7*

p4* _____ _____ p5*

E
p2 _____ _____ p3

p1 _____
Aromatic, Antiaromatic, Not Aromatic
• Hydrocarbons with the cycle conjugated
structures calls Annulenes

• An annulene compound can be Aromatic,

Antiaromatic, or Not aromatic
 Aromatic, Antiaromatic, Not Aromatic

Antiaromatic Not Aromatic

Aromatic

a cyclic, planar, completely cyclic, planar, completely a compound that lacks

conjugated with 4n + 2π conjugated compound one or more the
electrons with 4nπ electrons requirements for
aromaticity
Aromatic, Antiaromatic, Not Aromatic
• How about Cyclopentadiene and it’s ion
Aromatic, Antiaromatic, Not Aromatic
• How about Cyclopentadiene and it’s ion

Cyclopentadiene is not
an Aromatic compound
nor Antiaromatic
Aromatic, Antiaromatic, Not Aromatic
• How about Cyclopentadiene and it’s ion
Aromatic, Antiaromatic, Not Aromatic
• How about Cyclopentadiene and it’s ion

Antiaromatic Aromatic
 Aromatic Heterocycle

A cyclic compound that

Heterocyclic contains atoms of two
compounds can also be or more different
elements in its ring,
Aromatic usually carbon along
Heterocycle with nitrogen, oxygen,
or sulfur
 Aromatic Heterocycle

The nitrogen atom is also sp2-hybridized and has one electron in a p orbital, bringing the
total to six p electrons

Pyridin The nitrogen lone pair electrons are in an sp2 orbital in the plane of the ring and are not

e
involved with the aromatic p system
 Aromatic Heterocycle

Has two nitrogen atoms in a six-membered, unsaturated ring

Pyrimi Both nitrogens are sp2-hybridized, and each contributes one electron to the aromatic p

dine
system
 Aromatic Heterocycle

Pyrrole is a five membered heterocycle with six p electrons

Pyrrole Each of the sp2-hybridized carbons contributes one p electron

The sp2-hybridized nitrogen atom contributes the two electrons from its lone pair, which occupies a p orbital
 Aromatic Heterocycle

In pyridine and pyrimidine, the nitrogen atoms are both in

Nitrogen double bonds and contribute only one p electron to the
aromatic sextet, like a carbon atom in benzene does
atoms have
different roles
depending on In pyrrole, the nitrogen atom is not in a double bond
the structure and contributes two p electrons (the lone pair) to the
aromatic sextet
of the
molecule
 Aromatic Heterocycle

Thiophene is the sulfur analog of pyrrole

Thioph The sulfur atom is sp2-hybridized and has a lone pair of electrons in a p orbital perpendicular to the plane of the ring

ene Sulfur also has a second lone pair of electrons in the ring plane
 Conclution…
The Criteria of Aromaticity…

Cyclic Planar

Conjugate satisfy
d Huckel’s rule
Your Tasks Now…
 The Answers is…
1. a. b. c.

    - Cyclic   - Cyclic   - Cyclic

- Conjugated - Conjugated - Conjugated
- Hückle’s rule - Hückle’s rule - Hückle’s rule
- π electrons = - π electrons = 2 - π electrons = 4
2 - Aromatic - Aromatic
- Aromatic - Anti-aromatic - Anti-aromatic
- Anti-aromatic - Not aromatic - Not aromatic
- Not aromatic
 The Answers is…

2. - Cyclic
- Conjugated
- Satisfied the Hückle’s rule
- π electrons = 12
- Aromatic / Anti-aromatic / Not aromatic
 The Answers is…

3. - Cyclic
- Conjugated
- Satisfied the Hückle’s rule

O - π electrons = 6
- Aromatic / Anti-aromatic / Not aromatic
 The Answers is…

4. - Cyclic
N - Conjugated
- Satisfied the Hückle’s rule
- π electrons = 6
- Aromatic / Anti-aromatic / Not aromatic
 The Answers is…

5. - Cyclic
- Conjugated

N - Satisfied the Hückle’s rule

- π electrons = 10
H
- Aromatic / Anti-aromatic / Not aromatic
Conclution…
Thanks…