Aromaticity

hydrocarbons

aliphatic aromatic

alkanes alkenes 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 C—C bonds in benzene are the same length
and intermediate in length between single and double bonds.
a) Formula = C6H6
Max. number of H’s 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.

CH3C≡ C-C≡ CCH3 HC≡ C-C≡ C-CH2CH3

HC≡ CCH2C≡ CCH3 HC≡ CCH2CH2C≡ CH

 CH3
HC≡ CCHC≡ CH CH2=CHC≡ CCH=CH2

CH2=CHCH=CHC≡ CH CH2=C=CHCH2C≡ CH

CH3
CH2=C=CHC≡ CCH3 CH2=C=CC≡ CH

CH=CH2
CH2=C=CHCH=C=CH2 CH2=C
C≡ CH

CH3CH=C=CHC≡ CH
 CH2

=C=C=CH2
H2C 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.

CH3C≡ C-C≡ CCH3 HC≡ C-C≡ C-CH2CH3

 one possible three possibles

HC≡ CCH2C≡ CCH3 HC≡ CCH2CH2C≡ CH

three possible two possible
 CH3
HC≡ CCHC≡ CH CH2=CHC≡ CCH=CH2
three two +

CH2=CHCH=CHC≡ CH CH2=C=CHCH2C≡ CH
five + four +
CH3
CH2=C=CHC≡ CCH3 CH2=C=CC≡ CH
three + three +
CH=CH2
CH2=C=CHCH=C=CH2 CH2=C
four + C≡ CH four
+

CH3CH=C=CHC≡ CH four +
 CH2

one =C=C=CH2
possible
H2C CH2
two

CH2 CH2
=C=CH2
two +
CH2
three +

HC2= =CH2
two
 =CH2

three  one

two
There are three disubstituted benzenes of any
type: three dibromobenzenes C6H4Br2, etc.
CH2

CH3C≡ C-C≡ CCH3

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. Kekulé
(1890) proposed that the following were in rapid
equilibrium:
Br Br
Br Br
If benzene is 1,3,5-cyclohexatriene as Kekulé
proposed, what should its chemistry be? Alkenes,
dienes, cyclcoalkenes, etc. typically give addition
reactions with electrophiles.
But benzene doesn’t 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 C—C bonds in benzene are the same length and
intermediate in length between single and double bonds.

C—C single bonds ≈ 1.50 Å

C = C double bonds ≈ 1.34 Å
The bonds in benzene are all equal and 1.39 Å

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 C—C 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-]n-

HC CH
HC CH
4 pi electrons 6 pi electrons
8 pi electrons
aromatic

10 pi electrons 12 pi electrons
aromatic
 •

:
4 e- 4 e- aromatic 5 e-
6 e-

: •

does not have aromatic

p-orbitals on 8 e- 7 e-
all atoms 6 e-
Nomenclature for benzene:
monosubstituted benzenes:
Special names:
CH3 NH2 OH

toluene aniline phenol

CO2H SO3H

benzoic acid 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 m-chloronitrobenzene p-bromotoluene

1,2-dibromobenzene 3-chloro-1-nitrobenzene 4-bromotoluene

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

Br NH2
Br Br Br

Br
Br

1,2,4-tribromobenzene 2,4,6-tribromoaniline
 MD
MD MD
MD

MD
MD
orthodox
paradox metaphysicians

DDS DDS
DDS
DDS

orthodontists periodontists
Some other aromatic hydrocarbons:

napthalene anthracene phenanthrene

NOTE: H2
C
H2C CH2 C6H12
H2C CH2
C
H2
cyclohexane

H
C
HC CH C6H6
HC CH
C
H
benzene