Structure and Nomenclature of Aromatic Compounds

Historically, benzene-like substances were called aromatic hydrocarbons because they had distinctive aromas. Today, an aromatic compound is any compound that contains a benzene ring or has certain benzene-like properties (but not necessarily a strong aroma). You can recognize the aromatic compounds in this text by the presence of one or more benzene rings in their structure. Some representative aromatic compounds and their uses are listed in Table 1 , where the benzene ring is represented as C₆H₅.

In the International Union of Pure and Applied Chemistry (IUPAC) system, aromatic hydrocarbons are named as derivatives of benzene. Figure 1

shows four examples. In these structures, it is immaterial whether the single substituent is written at the top, side, or bottom of the ring: a hexagon is symmetrical, and therefore all positions are equivalent.

Figure 1 : Some Benzene Derivatives. These compounds are named in the usual way with the group that replaces a hydrogen atom named as a substituent group: Cl as chloro, Br as bromo, I as iodo, NO₂ as nitro, and CH₃CH₂ as ethyl.

Although some compounds are referred to exclusively by IUPAC names, some are more frequently denoted by common names, as is indicated in Table 1.

When there is more than one substituent, the corners of the hexagon are no longer equivalent, so we must designate the relative positions. There are three possible disubstituted benzenes, and we can use numbers to distinguish them (Figure 2). We start numbering at the carbon atom to which one of the groups is attached and count toward the carbon atom that bears the other substituent group by the shortest path.

Figure 2 : The Three Isomeric Dichlorobenzenes

In Figure 2 , common names are also used: the prefix ortho (o-) for 1,2-disubstitution, meta (m-) for 1,3-disubstitution, and para (p-) for 1,4-disubstitution. The substituent names are listed in alphabetical order. The first substituent is given the lowest number. When a common name is used, the carbon atom that bears the group responsible for the name is given the number 1:

Name each compound using both the common name and the IUPAC name.

1. 
2. 
3. 

Solution

1. The benzene ring has two chlorine atoms (dichloro) in the first and second positions. The compound is o-dichlorobenzene or 1,2-dichlorobenzene.
2. The benzene ring has a methyl (CH₃) group. The compound is therefore named as a derivative of toluene. The bromine atom is on the fourth carbon atom, counting from the methyl group. The compound is p-bromotoluene or 4-bromotoluene.
3. The benzene ring has two nitro (NO₂) groups in the first and third positions. It is m-dinitrobenzene or 1,3-dinitrobenzene.

Note: The nitro (NO₂) group is a common substituent in aromatic compounds. Many nitro compounds are explosive, most notably 2,4,6-trinitrotoluene (TNT).