12/8/2015

BENZENE
Marina Mokhtar
ENV 123 / ENV 124

Benzene and Aromatic Compounds

Benzene (C6H6) is the simplest aromatic hydrocarbon (or
arene).
Benzene has four degrees of unsaturation, making it a highly
unsaturated hydrocarbon.
Whereas unsaturated hydrocarbons such as alkenes, alkynes and
dienes readily undergo addition reactions, benzene does not.

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Benzene does react with bromine, but only in the presence of

FeBr3 (a Lewis acid), and the reaction is a substitution, not an
addition.

Proposed structures of benzene must account for its high degree

of unsaturation and its lack of reactivity towards electrophilic
addition.
August Kekul proposed that benzene was a rapidly equilibrating
mixture of two compounds, each containing a six-membered
ring with three alternating bonds.
In the Kekul description, the bond between any two carbon
3 atoms is sometimes a single bond and sometimes a double bond.

These structures are known as Kekul structures.

Although benzene is still drawn as a six-membered ring with alternating

bonds, in reality there is no equilibrium between the two different kinds of
benzene molecules.
Current descriptions of benzene are based on resonance and electron
delocalization due to orbital overlap.
In the nineteenth century, many other compounds having properties similar
to those of benzene were isolated from natural sources. Since these
compounds possessed strong and characteristic odors, they were called
aromatic compounds. It should be noted, however, that it is their chemical
properties, and not their odor, that make them special.
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Any structure for benzene must account for the following facts:
1. It contains a six-membered ring and three additional degrees
of unsaturation.
2. It is planar.
3. All CC bond lengths are equal.
The Kekul structures satisfy the first two criteria but not the
third, because having three alternating bonds means that
benzene should have three short double bonds alternating with
three longer single bonds.

The resonance description of benzene consists of two equivalent

Lewis structures, each with three double bonds that alternate
with three single bonds.
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 bonds.
We will use one of the two Lewis structures and not the hybrid
in drawing benzene. This will make it easier to keep track of the
electron pairs in the bonds (the electrons).

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Because each bond has two electrons, benzene has six

electrons.

Nomenclature of Benzene Derivatives

To name a benzene ring with one substituent, name the
substituent and add the word benzene.

Many monosubstituted benzenes have common names which

you must also learn.

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There are three different ways that two groups can be attached
to a benzene ring, so a prefixortho, meta, or paracan be
used to designate the relative position of the two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or
or
or
o-dibromobenzene
m-dibromobenzene
p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
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If the two groups on the benzene ring are different, alphabetize

the names of the substituents preceding the word benzene.
If one substituent is part of a common root, name the molecule
as a derivative of that monosubstituted benzene.

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For three or more substituents on a benzene ring:

1. Number to give the lowest possible numbers around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots, name the molecule as a
derivative of that monosubstituted benzene. The substituent that
comprises the common root is located at C1.

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A benzene substituent is called a phenyl group, and it can be

abbreviated in a structure as Ph-.

Therefore, benzene can be represented as PhH, and phenol

would be PhOH.

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The benzyl group, another common substituent that contains a

benzene ring, differs from a phenyl group.

Substituents derived from other substituted aromatic rings are

collectively known as aryl groups.

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Give the IUPAC name for each compound.

PhCH(CH3)2

isopropylbenzene

OH

m-butylphenol

Br

2-bromo-5-chlorotoluene
Cl

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What is the correct name for this compound?

A) 3-Nitrotoluene
B) 4-Nitromethylbenzene

O2N

C) p-Nitrotoluene
D) (4,1)-Methylnitrobenzene

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C) p-Nitrotoluene

What is the correct name for this compound?

A) 3,5-difluoroanisole

B) Difluoromethoxybenzene
O

C) 1,5-difluoro-3-methoxybenzene
D) 1,3-difluoro-5-methyl-O-benzene
F

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A) 3,5-difluoroanisole

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What is the correct name for this compound?

A) 4-bromo-m-xylene.

Br

B) 1-bromo-2,4-dimethylbenzene.
C) p-bromo-m-methyltoluene.
D) o-bromo-m-methyltoluene.

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B) 1-bromo-2,4-dimethylbenzene.

What is the correct name?

A) 1-fluoro-3-isopropyl-5-ethylbenzene

B) 1-ethyl-3-isopropyl-5-fluorobenzene
C) 1-ethyl-3-fluoro-5-isopropylbenzene
D) 1-isopropyl-3-fluoro-5-ethylbenzene

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C) 1-ethyl-3-fluoro-5-isopropylbenzene

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Which of these is aromatic?

CH2

A) Is aromatic. Count the number of pi bonds in the

outer ring. A has 5 which means 10 pi electrons,
4(2)+2=10. While B has 6 pi bonds and 12 pi electrons,
4(3)=12. Doesnt meet the Huckel rule requirements
for aromaticity.
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Industry

Made from Coal Tar (a liquid left over when coal is

heated) and Petroleum

Used as a Source for Almost all Aromatic Compounds

Make Complicated Aromatic Compounds by Taking

Benzene and Add on Other Rings Piece by Piece

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Industry - continued

Solvent for:

Sulfur, Phosphorus and Iodine

Gums

Fats, Waxes and Resins

Simple Organic Compounds

One of the Most Commonly Used Solvents in

Organic Chemistry
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Industry - continued
Can make Aniline and Phenol

Aniline:

Phenol:

Dye (Aniline Oil)

Disinfectant

Plastics

Antiseptic (Diluted)

Drugs (Sulfanilamide)

Insecticide

Explosives

Explosives

Detergent

Raw Material for

Aspirin
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Industry - continued

Makes Toluene, a component of TNT (Trinitrotoluene)

Makes Tear Gas

Makes Acetone

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Toxic Nature

Carcinogen -- Causes Leukemia

Makes Dioxins

Two Phenols Combine and Cl Connects to Make

Chlorinated Dibenzo-p-dioxin

Does not Dissolve in Water, but does in Oils and Fats

Accumulates in the Food Web

Mimics Hormones

Disrupts Normal Functions and Growth

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Chemical Reactions

Benzene

Nitration

Halogenation

Friedal Craft (Alkylation and Acylation)

Alkylbenzene

Oxidation

Halogenation (Free Radical and Substitution)

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Nitration

+ conc. HNO3 , conc. H2SO4

heated at 50 55 oC
NO2
conc. HNO3 , conc. H2SO4

50 - 55 C

H2 O

> 55 C

NO2

NO2

+
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NO2

O 2N

NO2

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Halogenation

+ Cl2 or + Br2

Need catalyst AlCl3 or Fe or FeCl3 (or FeBr3)

Cl

Cl2
FeCl3

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Alkylation (Friedal-Craft)

+ RCl or + RBr or + RI

Need catalyst AlCl3 , heat ()

CH 3

AlCl3

CH3Cl

HCl

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Acylation (Friedal Craft)

+ acyl chloride (R-COCl)

Need catalyst AlCl3 and heat

H3C
O

ii.

H3C C

AlCl3

O
C

Cl

HCl

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Oxidation

+ KMnO4 , acid (H+) and heat ()

COOH

CH3
KMnO4 , H+

H2O + CO2

CH3
H3C C CH3

** no reaction
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Halogenation (Free Radical)

+ Br2 , hv (uv)

H2C Br

CH3
Br2

HBr

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Halogenation (Substitution)

+ Cl2

Catalyst AlCl3

methyl (-CH3) is ortho, para directing

CH3

CH3
Cl2
AlCl3

CH3
Cl

+
Cl

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