Aromaticity

hydrocarbons

aliphatic

alkanes

alkenes

aromatic

alkynes

Aliphatic compounds: open-chain compounds and ring

compounds that are chemically similar to open-chain
compounds. Alkanes, alkenes, alkynes, dienes, alicyclics,
etc.

Aromatic compounds: unsaturated ring compounds that

are far more stable than they should be and resist the
addition reactions typical of unsaturated aliphatic
compounds. Benzene and related compounds.

Benzene. This aromatic hydrocarbon was first discovered in 1825 but

its structure was not generally agreed upon until 1946.

Facts about benzene:

a)

Formula = C6H6

b) Isomer number:
one monosubstituted isomer C6H5Y known
three disubstituted isomers C6H4Y2 known
c)

Benzene resists addition reaction, undergoes substitution reactions.

d) Heats of hydrogenation and combustion are far lower than they

should be.
e)

From X-ray, all of the CC bonds in benzene are the same length
and intermediate in length between single and double bonds.

a) Formula = C6H6
Max. number of Hs for 6-carbons = 14. Benzene only has 6
hydrogens. Given one degree of unsaturation (double bond or
ring) for every two missing hydrogens less than the maximum,
benzene has 4 degrees of unsaturation; that is four
combinations of pi-bonds and rings.

CH3CC-CCCH3

HCC-CC-CH2CH3

HCCCH2CCCH3

HCCCH2CH2CCH

CH3
HCCCHCCH

CH2=CHCCCH=CH2

CH2=CHCH=CHCCH

CH2=C=CHCH2CCH

CH2=C=CHCCCH3

CH3
CH2=C=CCCH
CH=CH2

CH2=C=CHCH=C=CH2

CH2=C
CCH

CH3CH=C=CHCCH

CH2

H2C

=C=C=CH2

CH2

CH2

CH2
=C=CH2
CH2
HC2=

=CH2

=CH2

Which of these structures is benzene?

b) Isomer number. There is only one monosubstituted

benzene of any type: only one bromobenzene C6H5Br,
only one nitrobenzene C6H5NO2, etc.

CH3CC-CCCH3
one possible

HCC-CC-CH2CH3
three possibles

HCCCH2CCCH3

HCCCH2CH2CCH

three possible

two possible

CH3
HCCCHCCH
three
CH2=CHCH=CHCCH
five +
CH2=C=CHCCCH3
three +
CH2=C=CHCH=C=CH2
four +

CH2=CHCCCH=CH2
two +
CH2=C=CHCH2CCH
four +
CH3
CH2=C=CCCH
three +
CH=CH2
CH2=C
CCH four +

CH3CH=C=CHCCH four +

CH2

H2C

CH2

one
possible

=C=C=CH2
two

CH2

CH2
=C=CH2
CH2

three +
HC2=

=CH2

two

two +

=CH2
three

one

two

There are three disubstituted benzenes of any

type: three dibromobenzenes C6H4Br2, etc.
CH2
CH3CC-CCCH3
two possible

CH2

CH2
four

four

Br

Br

Br

Br

Br

Br
Br
Br

No classical valence bond structure for C6H6 correctly

explains the existence of only one monosubstituted
benzene and three disubstituted benzenes. Kekul
(1890) proposed that the following were in rapid
equilibrium:
Br

Br

Br

Br

If benzene is 1,3,5-cyclohexatriene as Kekul

proposed, what should its chemistry be? Alkenes,
dienes, cyclcoalkenes, etc. typically give addition
reactions with electrophiles.
But benzene doesnt undergo the reactions typical of
unsaturated hydrocarbons!

Reagent

Cyclohexene

Benzene

KMnO4

oxidation

no reaction

Br2/CCl4

addition

no reaction

HI

addition

no reaction

H2/Ni

reduction

no reaction

Benzene + 3 H2, Ni, room temp. NR

Benzene +

3 H2, Ni, 200oC, 1500 psi cyclohexane

Although highly unsaturated, benzene does not react like

alkenes, dienes, cycloalkenes, or alkynes (addition
reactions) rather it undergoes substitution reactions
instead.

Reactions of benzene:
1. Nitration
C6H6 + HNO3, H2SO4 C6H5NO2 + H2O
2. Sulfonation
C6H6 + H2SO4, SO3 C6H5SO3H + H2O
3. Halogenation
C6H6 + X2, Fe C6H5X + HX
4. Freidel-Crafts alkylation
C6H6 + RX, AlCl3 C6H5R + HX
substitutions

d) Heats of hydrogenation and combustion are far lower than they should be.

cyclohexene + H2, Ni cyclohexane + 28.6 Kcal/mole

1,3-cyclohexadiene + 2 H2, Ni cyclohexane

55.4 Kcal/mole

(predicted value = 2 X 28.6 = 57.2 Kcal/mole)

benzene

3 H2, Ni, heat, pressure cyclohexane

49.8 Kcal/mole

(predicted value = 3 X 28.6 = 85.8 Kcal/mole)

Heat of hydrogenation for benzene is 36 Kcal/mole lower than predicted!

e) From X-ray, all of the CC bonds in benzene are the same length and
intermediate in length between single and double bonds.
CC single bonds 1.50
C = C double bonds 1.34
The bonds in benzene are all equal and 1.39
but 1,3,5-cyclohexatriene has
three double bonds and three
single bonds!

Resonance!
We can draw more than one classic
structure that differ only in where the
electrons are. The two structures are
of the same energy, so resonance is
important. The molecule cannot be
adequately represented by classic
structures but must be thought of as a
hybrid of the contributing structures.
Additionally, the hybrid is more
stable than any of the contributing
structures (resonance stabilization
energy).

Facts about benzene:

a)

Formula = C6H6

b) Isomer number:
one monosubstituted isomer C6H5Y known
three disubstituted isomers C6H4Y2 known
c)

Benzene resists addition reaction, undergoes substitution reactions.

d) Heats of hydrogenation and combustion are far lower than they

should be.
e)

From X-ray, all of the CC bonds in benzene are the same length
and intermediate in length between single and double bonds.

Aliphatic hydrocarbons are open-chain and ring compounds

that react like open chain compounds:
saturated: alkanes and cycloalkanes (typical reaction =
substitution)
unsaturated: alkenes, alkynes, dienes, cycloalkenes (typical
reaction = addition).
Aromatic hydrocarbons are unsaturated ring compounds
that resist the typical addition reactions of aliphatic
unsaturated compounds, instead undergoing substitution
reactions. They are also much more stable than they should
be.

Can we predict which compounds will be aliphatic and

which ones will be aromatic like benzene? Yes.
In order to be aromatic, the compound must be:
1) cyclic with p-atomic orbitals on all members of the
ring.
and
2) have 4i + 2 electrons in the p-orbitals of the ring
(where i = 0, 1, 2, 3, ).
[ eg. = 2 or 6 or 10 or 14 or 18 or 22 or 26 ]

pi-electrons sp2 hybridized carbons

p atomic orbitals

2 pi-electrons

.
0 pi-electrons

1 pi-electron

2 pi-electrons

annulenes: monocyclic compounds with the formula:

-[-CH=CH-]nHC CH
HC CH
4 pi electrons

10 pi electrons
aromatic

6 pi electrons
aromatic

8 pi electrons

12 pi electrons

4 e-

4 e-

aromatic

5 e-

6 e-

:
does not have
p-orbitals on
all atoms

aromatic

6 e-

8 e-

7 e-

Nomenclature for benzene:

monosubstituted benzenes:
Special names:
CH3

NH2

OH

toluene

aniline

phenol

CO2H

benzoic acid

SO3H

benzenesulfonic acid

others as substituted benzenes

Br

NO2

Cl

bromobenzene

nitrobenzene

chlorobenzene

Mercedes Benzene

Disubsituted benzenes:

ortho-

meta-

para-

1,2-

1,3-

1,4-

NO2

CH3

Br
Br

Cl
Br

o-dibromobenzene
1,2-dibromobenzene

m-chloronitrobenzene

p-bromotoluene

3-chloro-1-nitrobenzene

4-bromotoluene

If more than two groups on the ring, use numbers!

NH2

Br
Br
Br
1,2,4-tribromobenzene

Br

Br

Br
2,4,6-tribromoaniline

MD

MD

MD
MD
MD

MD
orthodox

paradox

DDS

metaphysicians

DDS
DDS
DDS

orthodontists

periodontists

Some other aromatic hydrocarbons:

napthalene

anthracene

phenanthrene

NOTE:
H2C
H2C

H2
C
C
H2

CH2
CH2

C6H12

CH
CH

C6H6

cyclohexane

HC
HC
benzene

H
C
C
H