1

Nomenclature: Arenes

• Arenes are named using the alkyl name of the substituent with benzene, so an arene
becomes an alkyl benzene.
• Compound 8 is named methylbenzene but its common name is toluene, a common
constituent of paint solvents.
• Similarly, compound 9 is ethylbenzene.
• Is the parent compound of 10 benzene, or is benzene a substituent? I
• In general, if a benzene ring is attached to an alkane carbon chain of five or
more carbon atoms, the benzene ring is treated as a substituent.
• 10 is named 2-phenylpentane.

8 9 10
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Nomenclature: Arenes

• Three dimethylbenzene derivatives are known: 1,2-dimethylbenzene (11), 1,3-

dimethylbenzene (12), and 1,4-dimethylbenzene (13).
• The common name for the dimethylbenzenes is xylene.
• In the common nomenclature, two substituents with a 1,2-relationship are said
to be ortho-; those with a 1,3-relationship are said to be meta-, and those with a
1,4-relationship are said to be para-.
• Using this system, 11 is called ortho-xylene (or o-xylene), 12 is called meta-xylene (or m-
xylene) and 13 is called para-xylene (or p-xylene).

CH3
CH3 CH3

CH3

CH3
CH3
11 12 13
14
Arene 14 is 1,2,4-trimethylbenzene.
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Nomenclature: Arenes

• 15 has an ethenyl group is known as ethenylbenzne, but the common

name is styrene.
• Compound 16 is E-1,2-diphenylethene but it is commonly called
trans-stilbene.
• Compound 17 is simply known as 1,2-diphenylethyne (or diphenyl
acetylene, although it has the common name of tolane).

15 16

C C

17
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Nomenclature: Functional Groups

• (18) is bromobenzene.
• 19 is named benzenol using the IUPAC system. The common name of
19 is phenol.
• 20 is 4-chlorobenzenol. 4-chlorophenol
• 21 is called methoxybenzene.
• 22 is ethoxybenzene.
• There are also common names for these compounds, so 21 is known an
anisole and 22 is phenetole.

Cl
Br OH OCH3 OCH2CH3

OH
18 19 20 21 22
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Nomenclature: Functional Groups

• Compound 23 is named benzeneamine, but the common name is

aniline, which is also an acceptable name.
• The name aniline or benzeneamine defines the class of compounds
bearing an -NR2 unit on a benzene ring.
• Substituents may appear on the benzene ring, as in 4-methylaniline
(24, 4-methylbenzeneamine), or on the nitrogen as in N-ethylaniline,
25 (N-ethylbenzeneamine).

NH2
NH2 NHEt

CH3
23 24 25
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Nomenclature: Functional Groups

• 26 is known as N-acetylaniline (N-acetylbenzeneamine; note that the

common name is acetanilide).
• Compound 27 is benzoic acid, the parent structure for this class, and
the usual acid derivatives such as esters (benzoates), acid chlorides
(benzoyl chlorides), and amides (benzamides) are all known.
• There are also nitrile derivatives, and 28 is named benzonitrile.

O
O OH
H C!N
H3C N

26 27 28
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Nomenclature: Functional Groups

• 29 is named benzenal. The common name is benzaldehyde.

• Acetophenone is the common name for 30, but the IUPAC name is 1-
phenylethanone.
• 31 is named 1-phenyl-1-butanone.
• An older system of nomenclature is available for such compounds, and 30 has been
named methyl phenyl ketone and 31 would be phenyl propyl ketone.
• 32is named benzophenone (if named as an aliphatic ketone, the name would be
diphenylmethanone).
• When both benzene rings of benzophenone are substituted, the name becomes a bit
more complicated. The substituent in one ring is numbered 1,2,3. etc., but the
substituents in the other ring are numbered with a "prime," such as 1', 2', 3', etc.
• Compound 33 is 4'-bromo-2,2',3-trimethylbenzophenone.

O H3C
O H O CH3 O
O

CH3 Br
CH3
29 30 31 32 33
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Nomenclature: Functional Groups

• (34) is named 1,2-benzenediol, but its common name is catechol.

• The meta- compound is named 1,3-benzenediol (resorcinol) and the para-
compound is named 1,4-benzenediol (hydroquinone).
• 1,2-Benzenedioc acid (phthalic acid, 35) has two carboxyl groups with an ortho-
relationship.
• In 1,3-benzenedioc acid (isophthalic acid), the carboxyl groups are meta-, and in
1,4-benzenedioc acid (terephthalic acid) the carboxyl groups have a para-
relationship.
• 1,2-benzenedial (phthaladehyde 36; also phthalic dicarboxaldehyde)
• 1,3-benzenedial (isophthalaldehyde; also isophthalic dicarboxaldehyde), and 1,4-
benzenedial (terephthalaldehyde; also terephthalic dicarboxaldehyde).

OH CO2H CHO
OH CO2H CHO

34 35 36
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Benzene as a Base

• It is known that benzene does not react directly with bromine, so it is easy to
conclude that it is a weak Lewis base as well as a weak Brønsted-Lowry base.
• It is known that diatomic bromine reacts with a Lewis acid such as ferric bromide
to generate an ate complex Br+ FeBr4–.
• If benzene is mixed with Br2, in the presence of ferric bromide (FeBr3), there is a
reaction and bromobenzene (18) is formed in good yield, along with HBr.

Br
Br2 Br2 , FeBr3
No Reaction

1 1 18

• Experiments have shown that the reaction proceeds by a cation intermediate (an
electrophilic reaction), and it clearly involves an aromatic species such as benzene.
• If benzene reacts with bromine via Br+, and there is a cation intermediate, it is
reasonable to conclude that the hydrogen atom is lost in a subsequent step.
• This type of reaction is labeled electrophilic aromatic substitution and it accounts
for most of the chemistry of benzene and its derivatives.
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Electrophilic Aromatic Substitution

• The reaction of diatomic bromine with aluminum chloride (AlCl3) gives complex
Br+AlCl3Br– as the product before there is any reaction with benzene.
• This cationic bromine atom is so reactive, however, that even a weak base like benzene will
react to form a carbocation, 40.
• This high energy intermediate is called a Wheland intermediate or an arenium ions
• 40 is reasonable stabilized as shown in 40A, which leads to sufficient stability that the
reaction generates this intermediate.
• 40 is resonance stabilized but not aromatic.
!+ !–
Br–Br AlCl3 Br+ AlCl3Br–
H H H H
H
Br Br Br Br
Br+
AlCl3Br–
39 1 40A
H Br
– H+
Br
AlCl3Br–
40C 18
40B