IUPAC Nomenclature of Aromatic Compounds

Aromatic compounds are compounds that contain a benzene ring and have a distinctive
aroma or odor. The molecular formula of benzene is C 6H6. Why? Because six carbon atoms
are attached cyclically, meaning in cycle, with three alternating pi bonds or the presence of
double bonds. Only one hydrogen atom is attached to each carbon atom. Below is the
illustration showing the structures of aromatic compounds.

Fig.1: Structures of Aromatic Compounds

How will you describe the structure of aromatic compounds? In the above
illustration, you will observe that the first structure of an aromatic compound has a hexagon
and alternating pi bonds or double bonds inside it. The double or pi bonds are arranged
alternately for the atoms to be stable. Another way of representing the benzene ring is
through the use of a hexagon with a circle or ring inside it. The corners represent the 6
carbon atoms. The last two structures of aromatic compounds where there is a circle at the
center of the hexagon symbolize that the pi bonds have no fixed position within the ring
because they keep on delocalizing to attain stability. You might question, why is the
hydrogen atom not found in the structure? Simply because aromatic compounds are
hydrocarbons; only carbon and hydrogen are attached to form a compound. It is understood
that only hydrogen atom is attached to carbon in the benzene ring so there is no need to
show it..
Just like other compounds, aromatic compounds are also named using the IUPAC
(International Union of Pure and Applied Chemistry) system. In this system, aromatic
hydrocarbons are named as derivatives of benzene to distinguish one from another.
Before you go through the different steps in naming Aromatic Compounds, you need
to be familiar with the symbols used for IUPAC Nomenclature.
1. Comma (,) is used to separate numbers. Example: 1,2
2. Hyphen/ dash (-) is used to separate numbers from names.
Example: 2-bromobenzene

Steps in Naming Aromatic Compounds

1. Aromatic Compounds with Single Substituent

a. When the substituent on the benzene ring is an alkane that has six or less than six
carbons, the name of the substituent is added as a prefix to benzene. Alkanes become an
alkyl group because they lose one hydrogen atom, their names end with –yl except for
methane (an alkane with one carbon).

Example: CH2CH3

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 ethylbenzene
b. When the substituent on the benzene ring is a halogen Br (bromine), F
(fluorine), Cl (chlorine), I (iodine); the name of the halogen is added as a prefix to
benzene but the ine is changed to o. When the substituent is NO2, it is nitro.

Example :
F NO2

fluorobenzene nitrobenzene

c. When common names are added as a substituent to the benzene ring,

common name becomes the parent molecule and will no longer be benzene.
(NOTE: You have to memorize this portion in order not to be confused.
CH3 OH NH2
Examples:

toluene phenol aniline

(not methylbenzene)

benzoic acid benzaldehyde

2. Aromatic Compounds with Two Substituents

Ortho, meta, and para are used as prefixes to lessen the numbering of the
substituents. Ortho (o-) for 1- 2 carbon placement, meta (m-) for 1-3 carbon
placement, and para (p-) for 1-4 carbon placement. Add the word di after prefix
ortho (o-), meta (m-) or para (p-) plus the name of the substituent if the substituent
appears twice; if the substituents are not the same arrange them in alphabetical
order.

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 Examples:

o-fluorotoluene p-difluorobenzene m -chloroiodobenzene

Why is it that the first example is named as o -fluorotoluene?

READ Here is the explanation : The name ends with toluene because there
is one methyl substituent attached to the benzene ring that indicates
the parent molecule is a toluene as stated in Step No.1 letter c.

3. Aromatic Compounds with Multiple Substituents

a. The location of each substituent is very important. Start numbering
the carbon atom to which the substituent is attached and count toward the carbon
atom that has the other substituent making sure that the sum of the locations gives
the smallest possible number. Arrange the
substituents in alphabetical order.
Example 1

5-bromo-2-chloro-1-ethylbenzene (Correct)

READ Explanation : Counting the location of carbon where the

substituent is attached in clockwise direction (1,2, and 5) gives a
sum of 8 which is lower than 10.

Example 2

3-bromo-6-chloro-1-ethylbenzene (Not Correct)

READ Explanation: Counting the location of carbon where the

substituent is attached in counter clockwise direction (1, 3, and 6)
gives a sum of 10 which is higher than 8.

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 b. If one of the substituents is a common name as stated in Rule No.1
letter c, the common name is used as the parent molecule and assigned as carbon
number 1. Arrange the substituents alphabetically. The direction of the numbering
for the rest of the substituents must give the sum of the lowest possible number.

Example

5-fluoro-2-nitrophenol

c. If the same substituent occurs not just twice , use prefix such as tri for
three or tetra for four. Do not include these prefixes in arranging the substituents
alphabetically.
Example:

1-bromo-2,4,5-trimethylbenzene

READ Explanation: Always consider the alphabetical arrangement of the

substituents, so, the numbering starts from bromine in counter
clockwise direction because it gives the sum of the location of the
substituents in smallest possible number (1+2+4+5=12).