Hckel's Rule

In 1931, Erich Hckel postulated that monocyclic (single ring) planar compounds that contained
carbon atoms with unhybridized atomic p orbitals would possess a closed bond shell of delocalized
electrons if the number of electrons in the molecule fit a value of 4 n + 2 where n equaled any whole
number. Because a closed bond shell of electrons defines an aromatic system, you can use Hckel's
Rule to predict the aromaticity of a compound. For example, the benzene molecule, which has 3
bonds or 6 electrons, is aromatic.

Number of electrons = 4 n + 2

6=4n+2

n=1
However, 1,3,5,7cyclooctatetraene, which has 4 bonds or 8 electrons, is not only nonaromatic but
is actually consideredantiaromatic because it is even less stable than the openchain hexatriene.

Number of electrons = 4 n + 2
8=4n+2
n = 1.5

Nomenclature
In IUPAC nomenclature, benzene is designated as a parent name. Other compounds that contain the
benzene molecule may be considered as substituted benzenes. In the case of monosubstitution (the
replacement of a single hydrogen), the prefix of the substituent is added to the name benzene.

In other cases, the substituent, along with the benzene ring, forms a new parent system.

When a benzene molecule is disubstituted (two hydrogens are replaced), two nomenclature methods
exist. Either a number system or name system indicates the relative position of one substituent to the
other. In the number system, one substituent is given the number one position and the second
substituent is assigned the lower possible second number. The number position is given to the atom or
group that has the higher priority as determined by the CahnIngoldPrelog nomenclature system
rules.

Notice that in the previous examples, the atom of the higher atomic weight is given the higher priority
(Br = 79.1 versus Cl = 15.5, and I = 126.0 versus N = 14.0). These assignments are based on
the priority rules of CahnIngoldPrelog nomenclature.
In the name system, one carbon atom containing a substituent is considered to be the initial (locator)
position. The carbon atom bonded to the other substituent is then located by the number of carbon
atoms separating it from the locator position, as shown in Figure 1.

The ortho position is one removed from the initial substituent's position. The meta
position is two removed, and the para is three removed.

Unlike the number system, you can assign an equally correct name with the names of the substituents
reversed.
Benzene compounds that contain three or more substituents are always named by the number
system. In this system, numbers are assigned to substituents so that the substituents have the lowest
possible combination of numbers.

Reactions of benzene

Although the resonance structures of benzene show it as a cyclohexatriene, because of its fully
delocalized system and the closed shell nature of this system, benzene does not undergo
addition reactions like ordinary unsaturated compounds. The destruction of the electron system
during addition reactions would make the products less stable than the starting benzene
molecule. However, benzene does undergo substitution reactions in which the fully delocalized
closed electron system remains intact. For example, benzene may be reacted with a halogen in
the presence of a Lewis acid (a compound capable of accepting an electron pair) to form a
molecule of halobenzene.