Naming Aromatic Compounds

(Benzene as the Parent)

If the the alkyl chain is smaller than the ring use the
ring as the parent
Monosubstituted benzenes named the same way
as other hydrocarbons using benzene as the
parent name

Aromatic Compounds
CH3

CH3

CH3

CH3

H3C

CH3

CH3
CH3
Common
Name

toluene

benzene

ortho-xylene

methylbenzene

IUPAC

CH3

meta-xylene

1,2-dimethylbenzene

cumene

para-xylene

1,3-dimethylbenzene

1,4-dimethylbenzene

isopropylbenzene

Other aromatic compounds:

OH

Cl

phenol

chlorobenzene

CH2OH

NH2

OMe

aniline

anisole

OH

SO3H

NO2

benzene
sulfonic acid
O

nitrobenzene

CH3

biphenyl
benzylalcohol benzaldehyde
or
phenylmethanol

benzoic acid

acetophenone

HC

CH2

styrene

More Aromatic Compounds

Polycyclic Aromatic Compounds
6
5
8

7
6
5

1
2

naphthalene

10

8
7

8
9

anthracene

10

phenanthrene

2,4,5,6,10-pentamethylphenanthrene

Heterocyclic Aromatic Compounds

O

H
N
N

furan

pyrrole

pyridine

N
pyrimidine

N
H
indole

Naming Aromatic Compounds

(Disubstituted Benzenes)

Relative positions on a benzene ring

ipso- carbon 1
ortho- (o) on adjacent carbons (1,2)
meta- (m) separated by one carbon (1,3)
para- (p) separated by two carbons (1,4)

N
H

N
N

purine

Naming Aromatic Compounds

(Benzenes with More Substituents)

Choose numbers for the lowest possible values

List groups alphabetically (hyphenated between)
numbers
Common names, such as toluene can serve as root
name (as in TNT)

Naming Aromatic Compounds

(Benzene as a Substituent)

If the the alkyl chain is larger than the ring use it as

the parent
When a benzene ring is a substituent, the term
phenyl is used (for C6H5)

You may also see Ph or or C6H5

Remember that benzyl refers to C6H5CH2

Structure of Benzene
H
H

H
H

All its C-C bonds are the same length (1.39 )

between length of normal single and double bonds

Electron density in all six C-C bonds is identical

Structure is planar

Stability of Benzene (Heats of Hydrogenation)

H2, Pd

H2, Pd

H2, Ni
175 C
180 atm

H2, Pd

Hexp = 28.6 kcal/mol

Hest = 57.2 kcal/mol

Hexp = 55.5 kcal/mol
= 1.7 kcal resonance energy
Hest = 85.8 kcal/mol
Hexp = 49.8 kcal/mol
= 36 kcal resonance energy

Hest = 85.8 kcal/mol

Hexp = 80.6 kcal/mol
= 5.2 kcal resonance energy

Aromaticity and the 4n + 2 Rule

1 monocyclic cmp

(i.e. don't look at anthracene, etc)

2 All atoms in the ring must have a p-orbital (sp2 atoms)

3 The p-orbitals must overlap...the cmp must be flat and the overlap
unbroken
4 -cloud must contain 4n+2 electrons (Hckel's Rule)
n = 0,1,2,3,4,5....
Therefore, compounds with 2,6,10,14,18 electrons will be aromatic
ALL the rules must be followed to be aromatic!
Huge energy advantage to being aromatic!

H H

sp3

Antiaromatic Compounds
1 monocyclic cmp

(i.e. don't look at anthracene, etc)

2 All atoms in the ring must have a p-orbital (sp2 atoms)

3 The p-orbitals must overlap...the cmp must be flat and the overlap
unbroken
4 -cloud must contain 4n electrons
n = 0,1,2,3,4,5....
Therefore, compounds with 4,8,12,16,20 electrons will be antiaromatic
ALL the rules must be followed to be antiaromatic!
Basically, nature avoids...use to explain why stuff doesn't happen
H

X
H

Aromatic Ions

Aromatic Heterocycles

A Heterocycle
is a cyclic
compound that
contains an
atom or atoms
other than
carbon

More Aromatic Heterocycles

O

Furan

Thiophene

Special Cases Pay Attention!

O

N
CH3

N
H3C

H
N
N

N
H

Special Compounds With 4n Electrons

4 electrons
antiaromatic
Exists @ 4 K

Cool Aromatic Compounds

azulene

Aromatic compounds composed smaller rings other

than benzene are called nonbenzenoid aromatic
compounds

H
H

B
N

H
N
B
H

H
B
N

Borazine
Discovered in 2009
21 kcal/mol resonance stabilization
Smells like benzene
17

Polycyclic Aromatic Compounds

(benzenoid)

Aromatic compounds can have rings that share a

set of carbon atoms (fused rings)
If they are composed of fused benzene rings they
are called benzenoid aromatic compounds
Some strange behavior: Not every ring is aromatic

What is Aromaticity?
MO Description of Benzene

Frost Diagrams

1. Inscribe the ring in a

concentric circle with
one of the points down
2. Draw energy levels at
each of the
intersections between
the circle and the ring
3. Cut circle in half
4. Fill the levels with
electrons starting at the
bottom and working
your way up

6e

non-bond MO's
bonding MO's

Why 4n+2?

Aromatic
NB

NB

Antiaromatic or Nonaromatic
NB

Diamond and Graphite

NB