BENZENE AND DERIVATIVES

MEMBERS GROUP :
NUR HIDAYAH BADARUDDIN
SYAZANA ISMAIL
NOOR AZURAH ABDUL RAZAK
IRA NUSRAT JAAFAR
NOR FADILAH ZAKARIA
 INTRODUCTION

• Benzene is a chemical that is a colourless or

light yellow liquid at room temperature. It
has a sweet odour and is highly flammable.
• Natural sources of benzene include volcanoes
and forest fires. Benzene is also a natural part
of crude oil, gasoline, and cigarette smoke.
Michael Faraday
• The word "benzene" derives
historically from "gum
benzoin", sometimes called
"benjamin" an aromatic resin
known to European pharmacists
and perfumers since the 15th
century as a product of southeast
Asia.
• Michael Faraday first isolated and
identified benzene in 1825 from
the oily residue derived from the
production of illuminating
gas, giving it the name bicarburet
of hydrogen.
 IUPAC
NOMENCLAT
URE
 a) MONOSUBSTITUTION
• 1) Benzene as the parent name:
ethylbenzene chlorobenzene bromobenzene
 2)Common name:

styrene cymene
toluene
3)Alkyl substituent is larger than ring:

3-phenyldecane

5-phenylpentanoic acid
 b) DISUBSTITUTION
• 1)Ortho- disubstituted benzene has two
substituent in a 1,2 positions:
• Principle functional group is the benzene
therefore root = benzene O-dichlorobenzene
• There are two chlorine
substituent therefore dichloro.
• The substituent locants are
1 and 2 therefore ortho.
2) Meta -disubstituted benzene has
two substituents in a 1,3 positions:
• Principle functional group is the benzne
therefore root = benzene m-bromochlorobenzene
• There is a chlorine substituent
therefore chloro.
• There is a bromine substituent
therefore bromo.
• The substituent locants are 1 and 3
therefore meta.
3) Para-disubstituted benzene has
two substituents in a 1,4 positions:
Polydisubstituted benzene
derivatives:
 c) POLYSUBSTITUTION
• Benzene with more than 2 substituents are
named by numbering the position of each
substituent with lowest possible numbers:
• Principle functional group is the aromatic amine
therefore = aniline
• There is a C1 substituent therefore methyl
• There is a C2 substituent therefore ethyl
• Numbering from the -NH2 (priority group at C1)
gives the substituents the locants =2 and 3
2-ethyl-3-methylaniline
Physical Properties
of Benzene
1.The Kekulé Structure of Benzene
• German chemist Friedrich August Kekulé von
Stradonitz
• A structure of benzene, containing 3 cyclic
conjugated double bonds which systematically
called 1,3,5-cyclohexatriene
Cont.

• The true structure of benzene is a resonance

hybrid of the two Lewis structures, with the
dashed lines of the hybrid indicating the
position of the π bonds.

hybrid
2.Stability
 Cont.
• Benzene does not undergo addition reactions typical of other highly
unsaturated compounds, including conjugated dienes.
• Benzene does not react with Br2 to yield an addition product. Instead, in the
presence of a Lewis acid, bromine substitutes for a hydrogen atom, yielding
a product that retains the benzene ring.
 3.Boiling Point
• The only attractions between neighbouring molecules are van der Waals
dispersion forces.
• Benzene boils at 80°C -

o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene

b.p. 1810C b.p. 1730C b.p. 1700C
 4. The Criteria for Aromacity :
Hückel's Rule

• 4 structural criteria must be satisfied for a

compound to be aromatic:
a) Cyclic
b) Planar
c) Completely Conjugated
d) Contain a particular number of π electrons
Cont.
[4] A molecule must satisfy Hückel’s rule, which requires a particular number
of  electrons.
Hückel's rule:

•Benzene is aromatic and especially stable because it contains 6  electrons.

•Cyclobutadiene is antiaromatic and especially unstable because it contains 4 

electrons.
Cont.

Note that Hückel’s rule refers to the number of  electrons, not the number of atoms in a
particular ring.
 Electrophilic Aromatic substituent

An electrophile (E⁺) reacts with an aromatic ring and substitutes

for one of the hydrogen

Benzene does not undergo addition reactions because addition

would yield a product that is not aromatic
 5 MAIN
ELECTROPHILIC
SUBSTITUENT
Step 1 : Formation of arenium ion
Positive ion X+ = electrophile

Example :

Step 2 : Loss of H +
Reactants : Benzene and halogens (Clorine or Bromine)
Conditions : Lewis acid like FeCl₃ or FeBr₃
Analogous reaction with I2 and F2 are not synthetically useful because I2 is
too unreactive and F2 is too violently
Electrophile : Cl⁺ or Br⁺
Example :

+ Br₂ no reaction
(decolorization not observed)

+
MECHANISM :

Step 1 : Formation of Cl⁺ or Br⁺

Step 2 : Electrophilic substitution

(The electrophile attacks the π electron system of the benzene ring

to form a arenium ion)
Step 3 : Loss of proton to reform the aromatic ring

bromobenzene

Function of Lewis acid :

Incerase the polarity of halogen molecules to produce positive
halogen ions (Cl⁺ or Br⁺) = electrophile
Reactants : Benzene and concentrated HNO₃
Conditions : Concentrated H₂SO₄

Example :

nitrobenzene
MECHANISM :
Step 1 : Formation of Nitronium ion (NO₂⁺)
- Sulfuric acid ionizes to produce a proton

-Nitric acid accepts a proton from a stronger acid (H₂SO₄) and

form a protonated nitric acid

- The protonated nitric acid dissociates to form a nitronium ion

(+NO2)
Step 2 : Electropjilic substitution

Step 3 : Loss of proton to re-form the aromatic ring

Reactants : Benzene and alkyl halide
Condition : catalyst (Lewis acid like AlCl₃)

+
Example :

1) AlCl₃

tolouene

2)

Tert-butylbenzene
MECHANISM :
Step 1 : Formation of carbocation

Step 2 : Electrophilic substitution

(electrophile attacks the π electron system of the benzene ring to
form an arenium ion)
Step 3 : loss of proton to re-form the aromatic ring
Friedel-Craft Acylation
Reactancts: Aromatic rings and acid chloride
Product: Ketone
Condition: Strong Lewis acid

AlCl3
Example:
Mechanism:
Step 1:
Dissociation of a chloride ion
to form an acyl cation
("acylium ion")

Step 2:
The resulting acylium ion or
a related adduct is subject
to nucleophilic attack by
the arene

Step 3:
Chloride anion (or AlCl4-)
deprotonates the ring (an
"arenium ion") to form
HCl, and the AlCl3 catalyst
is regenerated
Aromatic Sulfonation
Organic reaction in which a hydrogen atom on
an arene is replaced by a sulfonic acid
functional group in an electrophilic aromatic
substitution
Mechanism:

 Step 1:
The p electrons of the aromatic C=C act as a nucleophile, attacking the
electrophilic S, pushing charge out onto an electronegative O atom. This
destroys the aromaticity giving the cyclohexadienyl cation intermediate.

 Step 2:
Loss of the proton from the sp3 C bearing the sulfonyl- group reforms
the C=C and the aromatic system.

 Step 3:
Protonation of the conjugate base of the sulfonic acid by sulfuric acid
produces the sulfonic acid.
Substituent Effect in Substituted
Aromatic Benzene
 Ortho-Para

Orientation

Meta

Effect of
Substituent

Activating

Reaction Rate

Deactivating
Orientation

Para-substitution
Ortho-substitution-
2 substituents occupy Substituent occupy
positions next to positions 1 and 4
each other. Meta-substitution -
Substituent occupy
positions 1 and 3
Activating Group & Deactivating
Group
Ortho-Para Activator

 Electron donating groups (EDG) with lone pairs on the atoms

adjacent to the p system activate the aromatic ring by increasing
the electron density on the ring through a resonance donating
effect.
 The resonance only allows electron density to be positioned at
the ortho- and para- positions.
 Hence these sites aremore nucleophilic, and the system tends to
react with electrophiles at these ortho- and para- sites.
Examples:
Example:
Meta –Directing
Deactivator
 Meta-Directing

-COR
Deactivator increase -CO2R
-SO3H
-CHO
-CO2H
-CN
-NO2
-NR2+
 Explanation of meta- deactivators

Meta directors slow the reaction by raising the energy of the

carbocation intermediate because they have (in one resonance
form, shown below) a positively charged atom attached to the
ring. Two positively charged atoms so close together is very high
in energy (especially unstable).
SOME EXAMPLES OF "META DIRECTORS“

 the acyl group in benzaldehyde

 the NO2 group in nitrobenzene

acyl , -CN , -SO3H , CF3 , and -NO2 are meta directors and
deactivate the ring toward electrophilic aromatic substitution.
HALOGENATION OF ALKYLBENZENE SIDE CHAIN

Side chain bromination at the benzylic position occurs when aklybenzene is treated
with N-bromosuccinimide (NBS)
Mechanism of NBS (Radical) Reaction

•Abstraction of a benzylic hydrogen atom generates an intermediate benzylic radical

•Reacts with Br2 to yield product
•Br· radical cycles back into reaction to carry chain
•Br2 produced from reaction of HBr with NBS
Free radical also occurs between alkylbenzene side chain with halogen in the
presence of heat or light (hv)

CH3 hv CH2Cl
+ Cl2
OXIDATION OF ALKYLBENZENE

•Alkyl Benzene ring is inert to strong oxidizing agents such as KMnO4 and chromic
reagent
•side chains react readily with oxidizing agents are converted into carbonyl group
–COOH (Benzoic acid)

CH3 KMnO4 COOH

CH2 CH3 KMnO4 COOH

H3C CH3 KMnO4

COOH COOH