UNIT I

Benzene and its derivatives

Sub Topic: Structure of benzene

Presented by

[Link] Rao,[Link].,Ph.D
Professor & Head
Department of Pharmaceutical Chemistry
School of Pharmacy
Benzene has the molecular formula C6H6. From its elemental composition
and molecular weight, benzene was known to contain six carbon atoms and six
hydrogen atoms. The question was: how are these atoms arranged?
In 1858, August Kekule (of the University of Bonn) had proposed that
carbon atoms can join to one another to form chains. Then, in 1865, he offered
an answer to the question of benzene: these carbon chains can. sometimes be closed,
to form rings.
Benzene yields only one monosubstitution product, C6H5Y.
Only one bromobenzene, C6H5Br, is obtained when one hydrogen atom is replaced by bromine; similarly,
only one chlorobenzene, C6H5C1, or one nitrobenzene, C6H5NO2 , etc., has ever been made. This fact
places a severe limitation on the structure of benzene: each hydrogen must be exactly equivalent to every
other hydrogen, since the replacement of any one of them yields the same product.
Structure V, for example, must now be rejected, since it would yield two isomeric monobromo derivatives,
the 1-bromo and the 2-bromo compounds; all hydrogens are not equivalent in V. Similar reasoning shows
us that II and III are likewise unsatisfactory. (How many monosubstitution products would each of these
yield?) I and IV, among others, are still possibilities, however.
Benzene yields three isomeric disubstitution products, C6H4Y2 or C6H4YZ.
Three and only three isomeric dibromobenzenes, C6H4Br2 , three
chloronitrobenzenes,C6H4C1NO2, etc., have ever been made. This fact further limits
our choice of a structure; for example, IV must now be rejected. (How many
disubstitution products would IV yield ?)
At first glance, structure I seems to be consistent with this new fact; that is,
we can expect three isomeric dibromo derivatives, the 1,2- the 1,3-, and the 1,4-
dibromo compounds shown:
Resonance structure of benzene
The Kekule structure of benzene, while admittedly unsatisfactory, was generally
used by chemists as late as 1945. The currently accepted structure did not
arise from the discovery of new facts about benzene, but is the result of an extension
or modification of the structural theory; this extension is the concept of
resonance
The Kekule structures I and II, we now immediately recognize, meet the conditions for -resonance:
structures that differ only in the arrangement of electrons
Benzene is a hybrid I and II since I and II of exactly equivalent and hence of exactly the same
stability, they make equal contributions to the hybrid.
And, also since I and II are exactly equivalent, stabilization due to resonance should be large.

Orbital picture of benzene

A more detailed picture of the benzene molecule is obtained from a consideration of the bond orbitals in
this molecule.
Since each carbon is bonded to three other atoms, it uses sp2 orbitals These lie in the same plane, that of
the carbon nucleus, and arc directed toward the corners of an equilateral triangle. If we arrange the six
carbons and six hydrogens of benzene to permit maximum overlap of these
orbitals, we obtain the structure shown in Figure
Benzene is a flat molecule, with every carbon and every hydrogen lying in the same plane. It is a very
symmetrical molecule, too, with each carbon atom lying at the angle of a regular hexagon; every bond
angle is 120o. Each bond orbital is cylindrically symmetrical about the line joining the atomic nuclei
and hence, as before, these bonds are designated as a bonds.
There are still six electrons to be accounted for. In addition to the three orbitals already used, each carbon
atom has a fourth orbital, a p orbital. As we know, this p orbital consists of two equal lobes, one lying above
and the other lying below the plane of the other three orbitals, that is, above and below the plane of the ring;
it is occupied by a single electron. the orbital of any one carbon atom overlaps equally well the p orbitals of
both carbon atoms to which it is bonded. The result (see Fig. 10.3) is two continuous doughnut-shaped
electron clouds, one lying above and the other below the plane of the atoms.

it is the overlap of the p orbitals in both directions, and the resulting participation of each electron in several bonds that
corresponds to our description of the molecule as a resonance hybrid of two structures. Again it is the delocalization of
the n electrons their participation in several bonds that makes the molecule more stable.
To accommodate six electrons, there must be three orbitals . Their sum is, however, the symmetrical π clouds
we have described.
The orbital approach reveals the importance of the planarity of the benzene ring. The ring is flat because the
trigonal (sp2) bond angles of carbon just fit the 120 angles of a regular hexagon; it is this flatness that permits
the overlap of the p orbitals in both directions, with the resulting delocalization and stabilization.
The facts are consistent with the orbital picture of the benzene molecule. X-ray and electron diffraction show
benzene (Fig. 10.4) to be a completely flat, symmetrical molecule with all carbon-carbon bonds equal, and all
bond angles 120.
Despite delocalization, the π electrons are nevertheless more loosely held than the sigma electrons.
The π electrons are thus particularly available to a reagent that is seeking electrons: the typical
reactions of the benzene ring are those in which it serves as a source of electrons for electrophilic
(acidic) reagents. Because of the resonance stabilization of the benzene Ring, these reactions lead to
substitution, in which the aromatic character of the benzene ring is preserved

Representation of the benzene ring

For convenience we shall represent the benzene ring by a regular hexagon containing a circle (I); it
is understood that a hydrogen atom is attached to each angle of the hexagon unless another atom or
group is indicated.
I represents a resonance hybrid of the Kekule structures II and III. The straight lines stand
for the a bonds joining carbon atoms. The circle stands for the cloud of six delocalized n
electrons. I is a particularly useful representation of the benzene ring, since it emphasizes the
equivalence of the various carbon-carbon bonds. The presence of the circle distinguishes the
benzene ring from the cyclohexane ring, which is often represented today by a plain
hexagon.
Stability of the benzene ring.

The most striking evidence of this stability is found in the chemical reactions of benzene.
(a) Benzene undergoes substitution rather than addition.
Kekule's structure of benzene is one that we would call "cyclohexatriene." We would expect
this cyclohexatriene, like the very similar compounds, cyclohexadiene and cyclohexene,
to undergo readily the addition reactions characteristic of the alkene structure.
As the examples in Table show, this is not the case; under conditions that cause an alkene
to undergo rapid addition, benzene reacts either not at all or very slowly.

In place of addition reactions, benzene readily undergoes a new set of reactions,

all involving substitution.
 Stability of the benzene ring. Heats of hydrogenation
Heats of hydrogenation and combustion of benzene are lower than expected,
that heat of hydrogenation is the quantity of heat evolved when one mole of an unsaturated
compound is hydrogenated. In most cases the value is about 28-30 kcal for each double bond the
compound contains. It is not surprising, then, that cyclohexene has a heat of hydrogenation of
28.6 kcal and cyclohexadiene has one about twice that (55.4 kcal.) We might reasonably expect
cyclohexatriene to have a heat of hydrogenation about three times as large as cyclohexene, that is,
about 85.8 kcal. Actually, the value for benzene (49.8 kcal) is 36 kcal less than this expected
amount. This can be more easily visualized, perhaps, by means of an energy diagram (Fig. 10.1),
in which the height of a horizontal line represents the potential energy content of a molecule. The
broken lines represent the expected values, based upon three equal steps of 28.6 kcal. The final
product, cyclohexane, is the same in all three cases.
Aromaticity
Aromatic compounds as those that resemble benzene. But just which properties of benzene must a
compound possess following points

• Aromatic compounds are compounds whose molecular formulas would lead us to expect a high

degree of unsaturation

• Compounds posses the cyclic rings in their structures

• Posses the alternative double and single bonds in the structures

• which are resistant to the addition reactions generally characteristic of unsaturated compounds

• Instead of addition reactions, aromatic compounds undergo electrophilic substitution reactions

like those of benzene.

Modern concept of aromaticity or Huckle's rule

4n+2= 4
4n+2= 6 4n=4-2
4n=6-2 4n=2
4n=4 n=1/2
n=1
Benzene is aromatic
Reactions of Benzene and Its Derivatives

• Benzene does not undergo electrophilic addition

• It undergoes electrophilic aromatic substitution maintaining the

aromatic core

• Electrophilic aromatic substitution replaces a proton on benzene with

another Nucleophile
22
Electrophilic Aromatic Substitution