13.5.6 Directive influence of a functional group in monosubstituted benzene

When monosubstituted benzene is subjected to further substitution, three possible disubstituted products are not formed in equal amounts. Two types of behaviour are observed.

Either ortho and para products or meta product is predominantly formed. It has also been observed that this behaviour depends on the nature of the substituent already present in the benzene ring and not on the nature of the entering group. This is known as directive influence of substituents. Reasons for ortho/ para or meta directive nature of groups are discussed below:

Ortho and para directing groups: The groups which direct the incoming group to ortho and para positions are called ortho and para directing groups. As an example, let us discuss the directive influence of phenolic (–OH) group. Phenol is resonance hybrid of following structures:

It is clear from the above resonating structures that the electron density is more on o – and p – positions. Hence, the substitution takes place mainly at these positions.

However, it may be noted that –I effect of – OH group also operates due to which the electron density on ortho and para positions of the benzene ring is slightly reduced.

But the overall electron density increases at these positions of the ring due to resonance. Therefore, –OH group activates the benzene ring for the attack by an electrophile. Other examples of activating groups are –NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5, etc.

In the case of aryl halides, halogens are moderately deactivating. Because of their strong – I effect, overall electron density on benzene ring decreases. It makes further substitution difficult.

However, due to resonance the electron density on o– and p– positions is greater than that at the m-position. Hence, they are also o– and p– directing groups. Resonance structures of chlorobenzene are given below:

Meta directing group: The groups which direct the incoming group to meta position are called meta directing groups. Some examples of meta directing groups are –NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.

Let us take the example of nitro group. Nitro group reduces the electron density in the benzene ring due to its strong–I effect. Nitrobenzene is a resonance hybrid of the following structures.

In this case, the overall electron density on benzene ring decreases making further substitution difficult, therefore these groups are also called ‘deactivating groups’.

The electron density on o– and p– position is comparatively less than that at meta position. Hence, the electrophile attacks on comparatively electron rich meta position resulting in meta substitution.

 

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