Benzene and Its Derivatives

Aromatic Compounds
Aromatic compound: A hydrocarbon that contains one or
more benzene-like rings.
Arene: A term used to describe aromatic compounds.
• Ar-: A symbol for an aromatic group derived by
removing an -H from an arene.
• Kekulé structure for benzene (1872).
H
H C H
C C
C C
H C H
H
A Kek ulé structure A Kekulé structure
showing all atoms as a line-angle formula
Benzene
Resonance structure for benzene (1930s)
• The theory of resonance developed by Linus Pauling
provided the first adequate description of the structure
of benzene.
• According to the theory of resonance, certain
molecules and ions are best described by writing two
or more Lewis structures. The real molecule or ion is a
resonance hybrid of these structures.
• Each individual Lewis structure is called a contributing
structure.
• We show that the real molecule is a resonance hybrid
of the two or more Lewis structures by using a double-
headed arrow between them.
Benzene
• Here are two contributing structures for benzene;
H H
H C H H C H
C C C C
C C C C
H C H H C H
H H
• The resonance hybrid has some of the characteristics
of each Lewis contributing structure.
• The length of a carbon-carbon bond in benzene, for
example, is midway between that of a carbon-carbon
single bond and a double bond.
Nomenclature
• Monosubstituted alkylbenzenes are named as
derivatives of benzene; for example, ethylbenzene.
• The IUPAC system retains certain common names for
several of the simpler monosubstituted alkylbenzenes.
CH2 CH3 CH3 CH=CH2

Ethylbenzene Toluene Styrene

Nomenclature
• The common names for these monosubstituted
benzenes are also retained
O O
OH OCH3 NH2 C-H C-OH

Phenol A nisole A niline Benzaldehyde Benzoic acid

• Phenyl group (C6H5- or Ph-): The substituent group

derived by removal of an H from benzene.
4 2
3 1
C6 H5
Phenyl group 1-Phenylcyclohexene 4-Phenyl-1-butene
Nomenclature
When two substituents occur on a benzene ring, three
isomers are possible; they may be located by:
• numbering the atoms of the ring or
• using the locators ortho (o), meta (m), and para (p).
COOH CH2 CH3
CH3 4
1
2 Br 1
3
2

3 2
CH3 1
Cl
2-Bromobenzoic acid 1,3-D imethylbenzene 1-Chloro-4-ethylbenzene
(o-Bromobenzoic acid) (m-Xylene) (p-Chloroethylbenzene)
Nomenclature
For three or more substituents:
• If one of the substituents imparts a special name, name
the molecule as a derivative of that parent.
• If none of the substituents imparts a special name,
number the substituents to give the smallest set of
numbers, and list them in alphabetical order before the
ending "benzene".
CH3 OH NO2
1
2 NO2 Br 6
1
2 Br 4
3

2
3 5 3
4 4
1
Br
Cl Br CH2 CH3
4-Chloro-2- 2,4,6-Tribromophenol 2-Bromo-1-ethyl-4-
nitrotoluene nitrobenzene
PAHs
Polynuclear aromatic hydrocarbon (PAH)
• A hydrocarbon that contains two or more benzene
rings, with each pair of rings sharing two adjacent
carbon atoms.

Naphthalene Anthracene Phenanthrene Benzo[a]pyrene

Examples

First check to see if one of the substituents on the benzene ring

imparts a special name.
If one of them does, then name the compound as a derivative of that
parent molecule.
Examples
Write the names of the following compounds
note
Phenols
The functional group of a phenol is a hydroxyl ( -OH)
group bonded to a benzene ring.
• Name substituted phenols either as derivatives of
phenol or by common names.
OH OH OH OH OH
OH

OH
OH
Phenol 3-M ethylphenol 1,2-Benzenediol 1,3-Benzenediol 1,4-Benzenediol
(m-Cresol) (Catechol) (Resorcinol) (H ydroquinone)
Phenols
• Most phenols are weak acids, with pKa values
approximately 10.
• They are insoluble in water but react with strong bases,
such as NaOH and KOH to form water-soluble salts.
- +
OH + NaOH O Na + H2 O

Phenol Sodium Sodium phenoxide Water

hydroxide (w eaker base) pK a 15.7
pK a 9.95
(stronger base) (very soluble i n w ater) (w eaker acid )
(stronger aci d)
(onl y sl ightly
soluble i n w ater)
Phenols
Some phenols found in nature.
OH O
H3 CO CH OH

HO OH
2-Isopropyl-5- 4-H ydroxy-3-methoxy- CH2 (CH2 ) 1 1 CH3
methylphenol benzaldehyde Urushiol
(Thymol) (Vanillin) (Poison ivy)

O
CH3 O C
N
H
HO
Capsaicin
(from various types of peppers)
Phenols as Antioxidants
Autoxidation: A reaction that converts an R-H group to an
R-O-O-H (hydroperoxide).
H light O-O-H
CH2 CH=CH-CH + O2 CH2 CH=CH-CH-CH2
or heat
Section of a fatty Oxygen A hydroperoxide
acid hydrocarbon chain
Phenols as Antioxidants
Autoxidation is a radical chain reaction:
• Radical: An atom of molecule with an unpaired
electron.
• Chain initiation: Formation of a radical from a
nonradical compound.
H
light
CH2 CH= CH- CH CH2 CH= CH- CH
or heat
Section of a fatty A carbon radical
acid hydrocarbon chain
Phenols as Antioxidants
Chain propagation: Reaction of a radical to form a new
radical.
Propagation step 1:
O-O
CH2 CH=CH-CH + O-O CH2 CH=CH-CH
Oxygen is a
A hydroperoxy radical
diradical

• Propagation step 2:
O-O H
CH2 CH= CH- CH + CH2 CH= CH- CH
Section of a new fatty
acid hydrocarbon chain
O-O- H
CH2 CH= CH- CH -CH2 + CH2 CH= CH- CH
A hydroperoxide A new carbon radical
Phenols as Antioxidants
Hydroperoxides:
• Are unstable.
• Under biological conditions, they degrade to short-
chain aldehydes and carboxylic acids with unpleasant
"rancid" smells.
• Similar formation of hydroperoxides in the low-density
lipoproteins deposited on the walls of arteries leads to
cardiovascular disease in humans.
• In addition, many effects of aging are thought to be the
result of hydroperoxide formation and their subsequent
degradation.
Phenols as Antioxidants
• Vitamin E is a natural antioxidant.
• BHT and BHA are synthetic antioxidants.
OH OH
O
H
3
HO
OCH3
Vitamin E Butylated hydroxy- Butylated hydroxy-
toluene (BHT) anisole (BHA)

• These compounds are radical scavengers.

• They form stable radicals and thus break the cycle of
chain propagation steps; they prevent further
formation of destructive hydroperoxides.