Chapter 4

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BENZENE

AROMATIC HYDROCARBON
Aromatic Compounds

Benzene is
• An aromatic compound.
• a ring of 6 C atoms and 6 H atoms.
• a flat ring structure drawn with three double
bonds.
Benzene
• Kekule suggested two structural formulas for benzene:

• The empirical formula (CH) and molecular formula


(C6H6) indicate a highly unsaturated hydrocarbon
(double bonds).

• Hydrogenation of benzene gives cyclohexane. Thus, the


six C atoms are joined in a ring.
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) Physical properties similar to other hydrocarbons

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.
Resonance Structures
• There are two ways to write the structure of benzene
• These are called “resonance structures”
• However, neither of these represents the true structure of
benzene since benzene has only one structure, with all C-C
bonds being equivalent
• The true structure is a hybrid of the the two resonance
structures; this can be represented by drawing the  bonds as a
circle
• We use the individual resonance structures when we write
reaction mechanisms involving benzene to show more clearly
the bond formation and bond breaking in the reaction
Physical Properties

1. It is a colourless liquid with boiling point


80oC.
2. It is insoluble in water but soluble in organic
solvent.
3. It burns with a sooty flame and it is highly
inflammable.
4. It is carcinogenic.
PHYSICAL PROPERTIES
Melting points, boiling points, level of solubility
in water
• As the length of carbon chain increases,
boiling/melting point increases. (for
compounds with identical functional groups)
• As the length of carbon chain increases,
solubility decreases
Nomenclature of Benzene
• Benzene Derivatives
The nomenclature of substituted benzene ring compounds
is less systematic than that of the alkanes and alkenes.

A few mono-substituted compounds are named by using a


group name as a prefix to "benzene“.

A majority of these compounds, however, are referred to by


singular names that are unique.
IUPAC Naming
CH2 CH3 CH3 CH=CH2

Parent name

Eth ylb enzene Toluen e Styrene


Aromatic compounds are named:

• With benzene as the parent chain.


• Name of substituent comes in front of the “benzene”.

CH32 CH3
CH CH2 CH3
CHCl CH=CHCHCH
CH2-CH
CH33 CH=CHC
3 2 3 2 2

methylbenzene
Eth ylb enzene Eth ylbeenzene
chlorobenzene
Toluen Toluen
Eth ylb
e enzene Styrene
ethylbenzene
Styrene Tolu
Two commonly encountered substituent groups that
incorporate a benzene ring are phenyl, and benzyl.

A general and useful generic notation that complements the


use of R- for an alkyl group is Ar- for an aryl group (any
aromatic ring).
In the case of disubstituted benzenes, the prefixes ortho,
meta & para are commonly used to indicate a 1,2- or 1,3-
or 1,4- relationship respectively.
Some disubstituted toluenes have singular names (e.g.
xylene, cresol & toluidine) and their isomers are normally
designated by the ortho, meta or para prefix.
if there are three or more substituent groups, the ring is
numbered in such a way as to assign the substituents the
lowest possible numbers.
Common Nomenclature in Substituted Benzenes

ortho , meta and para Positions


CH3

m-nitrotoluene
R ipso NO2

ortho
o- 1-methyl-3-nitro-benzene

meta Cl
m-

p- para p-dichlorobenzene

Cl
1,4-dichlorobenzene
WWU -- Chemistry
Naming Multisubstituted Benzene Compounds
• When there are 2 or more substituents, they are numbered to
give the lowest numbers (alphabetical if same both ways)
• Disubsituted benzenes are also named by the common prefixes
ortho, meta and para

Examples:
Br CH3

Cl

Br

meta-dibromobenzene ortho-chlorotoluene
(1,3-dibromobenzene) (1-chloro-2-methylbenzene)

OH NH2

Br

para-ethylphenol 4-bromo-2-fluoroanaline
(1-hydroxy-4-ethylbenzene) (1-amino-4-bromo-2-fluorobenzene)
Electrophilic Aromatic Substitution

• Electrophilic aromatic substitution:

H E
+ E+ + H+
Mechanism of Bromonation of Benzene
• First, a Br+ is transferred from Br2 to benzene, forming a
carbocation and a chloride ion
• Next, the chloride ion removes an H+ from the carbocation
to form chlorobenzene and HBr

Br
H
FeBr3
+ Br Br + Br

Br
H Br

+ Br + H Br
Halogenation
• In halogenation, benzene reacts with Cl2 or Br2 in the presence
of a Lewis acid catalyst, such as FeCl3 or FeBr3, to give the aryl
halides chlorobenzene or bromobenzene respectively.
• Analogous reactions with I2 and F2 are not synthetically useful
because I2 is too unreactive and F2 reacts too violently.
Halogenation of Benzene

H X
FeX3
+ X2 + H X

•X can be either bromine or chlorine


•Other catalysts might include elemental iron (Fe0 or
aluminum chloride (AlCl3)
•The ferric halide serves to generate the electrophile in this
reaction.
Formation of the Halonium Ion

X2 + FeX3 X FeX4

a "stable" complex
•X+ is a halonium ion:
•Cl+ = chloronium ion
•Br+ = bromonium ion
•The halonium ion is the electrophile in this reaction.
Addition reaction

Halogenation
Cl
Cl Cl
u.v.
+ 3Cl2
Cl Cl
Cl

It is the free radical addition reaction.


The 1,2-dichlorocyclohexa-1,3-diene cannot be the
final product since it is more reactive than the benzene
(as the resonance structure is broken).
Therefore, further addition reaction is expected and
the product is hexachlorohexane.
Chemical properties
Electrophilic aromatic substitution

(i) Halogenation
ArH reacts with halogen (X2), in the presence of a Lewis acid
catalyst (AlX3 or FeX3).

(ii) Nitration
ArH reacts with concentrated nitric acid (HNO3), in the presence
of concentrated sulphuric acid (H2SO4) as a catalyst, to form
nitrobenzene (ArNO2).
(iv) Friedel-Craft alkylation
ArH reacts with haloalkanes (RX), in the presence of
Lewis acid catalyst (AlX3 or FeX3), to form alkylarene (Ar-
R). The electrophile is alkylcarbocation (R+).

(v) Friedel-Craft acylation


ArH reacts with acyl chlorides (RCOCl), in the presence of a
Lewis acid catalyst (AlCl3 or FeCl3), to form acylbenzene
(RCOAr). The electrophile is acylium ion (RCO+).
The Friedel-Crafts Acylation Reaction

H C R

AlCl3
+
+
O
H X
R C Cl

The product is an acylbenzene (aromatic ketone)


The Friedel-Crafts Acylation Reaction

• The role of the anhydrous aluminum


chloride is to generate a stable carbocation
complex.
• The carbocation is the electrophile in this
process.
• In this case, the carbocation is an acylium
ion.
(vi) Hydrogenation
Benzene is very difficult to hydrogenate because of stable
aromatic system.
To hydrogenate, benzene requires a highly active catalyst
and high temperature and pressure.

H2
Pt/Ni/Pd
CHARACTERIZATION TEST
Nitration of benzene
Reagent: concentrated HNO3
Condition: concentrated H2SO4, 55°C
Equation:
+ conc HNO3 H2SO4
+ HO
2
55 C

NO2

Observation: yellowish oil with almond smell is


produced for benzene.
Reactivity towards electrophilic aromatic substitution

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