BENZENE

Index
Introduction
Characteristics of benzene
Nomenclature in aeromatic compound
Structure of Benzene
Stability of Benzene (Resonance)
Properties of Benzene

Reaction of Benzen
Nitration of benzene
Friedel Craft Alkylation
Friedel Craft Acylation:
Physical properties
Boiling point
Melting point
Soluility in water
Benzene-derivatives
Benzene-uses
Health issues
 Introduction to Benzene (C6H6)

The term aromatic (Greek; aroma means fragrance) was first used for compounds having
pleasant odour although the structure was not known. Now the term aromatic is used for a class of
compounds having a characteristic stability despite having unsaturation. These may have one or
more benzene rings (benzenoid) or may not have benzene ring
Simplest organic, aromatic hydrocarbon and parent compound of numerous important
aromatic compounds. Benzene is a colourless liquid with a characteristic odour and is primarily
used in the production of polystyrene. It is highly toxic and is a known carcinogen; exposure to it
may cause leukemia. As a result, there are strict controls on benzene emissions.
Discovery of benzene:-
Benzene was first discovered by the English scientist Michael Faraday in 1825 in illuminating
gas. In 1834 German chemist Eilhardt Mitscherlich heated benzoic acid with lime and produced
benzene. In 1845 German chemist A.W. von Hofmann isolated benzene from coal tar.
The structure of benzene has been of interest since its discovery. German chemists Joseph
Loschmidt (in 1861) and August Kekule von Stradonitz (in 1866) independently proposed a cyclic
arrangement of six carbons with alternating single and double bonds. Kekule subsequently
modified his structural formula to one in which oscillation of the double bonds gave two
equivalent structures in rapid equilibrium. In 1931 American chemist Linus Pauling suggested that
benzene had a single structure, which was a resonance hybrid of the two Kekule structures.

Joseph Loschmidt's structure

Kekule's structure
 Characteristics of benzene

Experimental studies, especially those employing X-ray diffraction, show benzene to

have a planar structure with each carbon-carbon bond distance equal to 1.40 angstroms
(). This value is exactly halfway between the C=C distance (1.34 ) and CC distance (1.46
) of a C=CC=C unit, suggesting a bond type midway between a double bond and a single
bond (all bond angles are 120). Benzene has a boiling point of 80.1 C (176.2 F) and a
melting point of 5.5 C (41.9 F), and it is freely soluble in organic solvents, but only slightly
soluble in water.
Modern bonding models (valence-bond and molecular orbital theories) explain the
structure and stability of benzene in terms of delocalization of six of its electrons, where
delocalization in this case refers to the attraction of an electron by all six carbons of the
ring instead of just one or two of them. This delocalization causes the electrons to be more
strongly held, making benzene more stable and less reactive than expected for an
unsaturated hydrocarbon. As a result, the hydrogenation of benzene occurs somewhat
more slowly than the hydrogenation of alkenes (other organic compounds that contain
carbon-carbon double bonds), and benzene is much more difficult to oxidize than alkenes.
Most of the reactions of benzene belong to a class called electrophilic aromatic
substitution that leave the ring itself intact but replace one of the attached hydrogens.
These reactions are versatile and widely used to prepare derivatives of benzene.
 Nomenclature of aeromatic compound

Trivial names are more commonly used for aromatic compounds than is the case with other
compound families in organic chemistry. Though trivial names are not recommended, IUPAC rules
allow their use with common aromatic compounds, such as methylbenzene (toluene),
hydroxybenzene (phenol), and aminobenzene (aniline).
Monosubstituted benzene derivatives are named by analogy with other hydrocarbons -
with benzene as the parent name.

Systematic Nomenclature of Aromatic Compounds

Analogous to alkanes, alkenes, and alkynes, alkyl-substituted benzenes are also
called arenes. The aromatic C6H5- residue is called phenyl. The name depends on the
length of the alkyl substituent. If the substituent contains no more than six carbon atoms,
the compound's parent name is benzene. This would then be classified as an alkylbenzene,
such as is the case with ethylbenzene and 2-pentylbenzene. However, if the alkyl
substituent possesses more than six carbon atoms, the compound is considered to be a
phenylalkane (or -alkene, or -alkyne, respectively), such is the case with 3-phenyloctane.
Above all in empirical and structural formulas, the phenyl group is often abbreviated by
"Ph". The namephenyl derives from the Greek word "phainein" (= shine), as Michael
Faraday first discovered phenol in the liquid residue that condensed from the gas phase in
London's street lamps when whale oil was burnt. The C6H5CH2- residue is called benzyl.

The different dihydroxybenzenes display different chemical properties

catechol
hydroquinone
resorcinol

Nomenclature of Polysubstituted Aromatic Compounds:-

The relative position of substituents in double-substituted benzenes is indicated by
the prefixes ortho(o), meta (m) and para (p). The substituent's relative position in ortho-
substituted benzenes is "1,2". It is "1,3" in meta-substituted benzenes and "1,4" in para-
substituted benzenes. The prefixes ortho, meta, and para, or their abbreviations o,m, and
p, respectively, are written in italics when used with compound names.

o,m,p-Nomenclature is also commonly used in describing the reactions and their

mechanisms of aromatic compounds, when the position in which the reaction takes place
must be specified, such as is the case in the sentence "In the catalytic bromination of
toluene, bromine reacts in para position...".

Benzene derivatives with more than two substituents are named systematically
through the numeration of the substituents' positions. The position numbers must be
determined so that they are as small as possible. In the compound name, the substituent
names are arranged alphabetically and are prefixed to the parent name.

It is common usage and allowed to use other parent names as benzene,such as

toluene , phenol and benzoic acid.
 Structure of Benzene
Benzene has been known since 1825 when it was first isolated by Michel Faraday.
Form elemental analysis and molecular mass determination, it was found that the
molecular formula of benzene is C H indicating high unsaturation. However, benzene does
undergo addition reactions in contrast to unsaturated hydrocarbons, although it mainly
undergoes substitution reactions. In 1865 Friedrich August Kekule proposed a ring
structure for benzene (I). However, many alternative structures have been proposed from
time to time by different workers. (II-IV).Then main objection against Kekule structure was
that it should
yield two ortho disubstituted products when it reacts with bromine. However,
experimentally benzene was found to yield only one product. Kekule removed this
objection by proposing that the double bonds in benzene are continuously oscillating back
and forth between two adjacent positions. Since positions of double bonds are not fixed,
only one product is formed. This structure came to be known as Kekules dynamic formula,
which formed the basis for the present electronic structure of benzene.

Stability of Benzene (Resonance)

Benzene resists addition whereas it readily undergoes substitution reactions, like
nitration, halogenation etc. This indicates that benzene is more stable than the
hypothetical cyclohexatriene molecule. This has been proved by the fact that the
enthalpies of hydrogenation and combustion of benzene are lower than expected. Enthalpy
of hydrogenation is the change in enthalpy when one mole of an unsaturated compound is
hydrogenated. It has been found experimentally that enthalpy of hydrogenation for
disubstituted alkenes, R-CH=CH-R varies between 117-125 kJ mol . Accordingly, the values
for cyclohexene and cyclohexa-1, 3-diene and hypothetical cyclohexa-1, 3, 5-triene were
calculated compared with their experimental values While the experimental values of
enthalpy of hydrogenation for cyclohexene is similar to the value expected, the variation in
the case of cyclohexa-1, 3-diene is small and is due to delocalization.
The expected value of enthalpy of hydrogenation of benzene is much higher than
the corresponding calculated value for hypothetical cyclohexa-1, 3, 5-triene indicating that
benzene does not have this type of structure. X-ray studies show that it is planar molecule
and that all six C-C bonds in benzene are of equal length (139 pm), intermediate between
C-C single bond (154 pm) and C=C (134 pm). All six carbons are sp hybridized and all bond
angles are 120 . Benzene is a hybrid of various resonating structures, the two Kekule
structures A and B, being the main contributing forms.
 Properties of Benzene

1. It is a colourless liquid with boiling point of 80 0C.

2. It is inflammable, burning with a smoky flame due to high carbon content.
3. It is slowly attacked by acid permanganate to form CO2 and H2O.

4.

5.
 Reactions of Benzene

Major reactions of benzene ring are electrophilic substitution reactions.

1. Niration of benzene:
Formation of electrophile NO2+:-

Electrophilic attack by NO2+:-

Loss of proton:-

2. Friedel Craft Alkylation:

This reaction involves the introduction of alkyl group into benzene ring in
presence of catalyst.The alkylating agent may be R X, ROH or alkene. The catalyst is a
Lewis acid BF3,AlCl3,H2SO4 or H3PO4.
Mechanism:

Step I:

Formation of electrophile (carbonium ion) stability order of carbonium ion is

With RX

With ROH:

With alkene:

Step II:

Step III:
3. Friedel Craft Acylation:
Replacement of H+of benzene by RCO- group using carboxylic acid, esters, acid
chloride or acid anhydride as acylating agent in the presence of Lewis acid.

Mechanism:
(i)

(II) is more stable than (I) because each atom has a complete octet.

(ii)

(iii)

Examples:
 Physical properties

1. Boiling point
In benzene, the only attractions between neighbouring molecules are vander
Waals dispersion forces. There is no permanent dipole on the molecule.

Benzene boils at 80C - rather higher than other hydrocarbons of similar

molecular size (pentane and hexane, for example). This is presumably due to the
ease with which temporary dipoles can be set up involving the delocalised
electrons.

Methylbenzene boils at 111C. It is a bigger molecule and so the van der Waals
dispersion forces will be bigger.

Methylbenzene also has a small permanent dipole, so there will be dipole-dipole

attractions as well as dispersion forces. The dipole is due to the CH3 group's
tendency to "push" electrons away from itself. This also affects the reactivity of
methylbenzene.

2. Melting point
You might have expected that methylbenzene's melting point would be higher
than benzene's as well, but it isn't - it is much lower! Benzene melts at 5.5C;
methylbenzene at -95C. Molecules must pack efficiently in the solid if they are
to make best use of their intermolecular forces. Benzene is a tidy, symmetrical
molecule and packs very efficiently.

The methyl group sticking out in methylbenzene tends to disrupt the closeness
of the packing. If the molecules aren't as closely packed, the intermolecular
forces don't work as well and so the melting point falls.

3. Solubility in water
The arenes are insoluble in water.

Benzene is quite large compared with a water molecule. In order for benzene to
dissolve it would have to break lots of existing hydrogen bonds between water
molecules. You also have to break the quite strong van der Waals dispersion forces
between benzene molecules. Both of these cost energy.

The only new forces between the benzene and the water would be van der Waals
dispersion forces. These aren't as strong as hydrogen bonds (or the original
dispersion forces in the benzene), and so you wouldn't get much energy released
when they form.
 benzene-derivatives
A number of the substituted benzene derivatives are well known and commercially
important compounds. For example, the substitution of a single methyl, hydroxyl, or amino
group in benzene results in the formation, respectively, of toluene (C6H5CH3), phenol
(C6H5OH), or aniline (C6H5NH2). Probably the best known disubstituted products are the
xylenes, C6H4(CH3)2. Three different xylene molecules are possible depending on whether
the methyl groups are adjacent to each other on the benzene ring (ortho-xylene),
separated by one carbon atom (meta-xylene), or opposite each other on the ring
(paraxylene). The removal of one hydrogen atom from the benzene molecule results in a
radical known as the phenyl group.
Benzene occurs so abundantly in and is obtained so easily from coal tar and
petroleum that there is virtually no reason to make it synthetically. Although benzene had
been recognized as a component of petroleum for many years, it was not produced
commercially from that source until the beginning of World War II.

benzene-uses
Benzene is used as a solvent in many commercial, industrial, and research
operations. It has long been of interest as a fuel because of its high octane number. Some
manufacturers, particularly in Europe, have used it as a gasoline additive to increase engine
efficiency and to improve starting qualities.

By far the most important use of benzene, however, is in the production of other
aromatic compounds. The word aromatic was originally applied to benzene because of its
distinctive odor, but it later took on a broader meaning, referring to any compound whose
molecular structure includes one or more benzene rings. The largest volume of compounds
made from benzene goes toward the production of commercially valuable polymers, such
as polystyrene, nylon, and synthetic rubber.

The benzene derivative produced in largest quantity is ethylbenzene (C6H5C2H5).

Ethylbenzene is converted to styrene (C6H5CH=CH2) which, in turn, is polymerized to form
polystyrene. Nearly half of all benzene used in chemical synthesis is used for this process.

In another example, benzene is treated with propylene to form cumene

(C6H5CH[CH3]2). The cumene thus formed is then oxidized to produce phenol. Phenol is
the starting point for a large number of polymers known as phenolic resins.

Synthetic fibers are produced by yet a third kind of benzene substitution sequence.
The addition of hydrogen to benzene converts it to cyclohexane (C6H12), which is then
oxidized to adipic acid (COOH[CH2]4-COOH) The acid can then be treated with
hexamethylene diamine to form nylon.
 Health issues
The health risks associated with exposure to benzene have been known for many
years. The compound has both chronic and acute effects whether ingested by mouth,
taken in through the respiratory system, or absorbed through the skin. Acute effects
resulting from inhalation include irritation of the mucous membranes, headache,
instability, euphoria, convulsions, excitement or depression, and unconsciousness. The
ingestion of benzene has been associated with the development of bronchitis and
pneumonia, while exposure through the skin can cause drying, blistering, and erythema
(redness). Death can result from exposure to high concentrations of benzene. Chronic
effects resulting from benzene exposure include reduced white and red blood cell counts,
aplasia, and more rarely, leukemia.

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