18.12 : Directing Effect of Substituents: ortho–para-Directing Groups

Ortho–para directors are substituent groups attached to the benzene ring and direct the addition of an electrophile to the positions ortho or para to the substituent. All electron-donating groups are considered ortho–para directors. They donate electrons to the ring and make the ring more electron-rich. The ring is therefore susceptible to the addition of electrophiles. Substituents such as amino, hydroxy, or alkoxy, containing lone pairs on the atom adjacent to the ring, donate electrons through resonance. For instance, phenol can undergo nitration at either ortho, meta, or para positions. However, the ortho and para carbocation intermediates are more stable than the meta intermediate because they have more resonance forms. Moreover, a particular favorable form in ortho and para carbocation intermediates exists—the one arising from the donation of oxygen’s nonbonding electrons.

Alkyl substituents without lone pairs also function as ortho–para directors. They donate electrons through an inductive effect. The carbocation intermediates involved in the ortho–para attack are more stable than meta. The ortho–para directors function by stabilizing a positive charge directly on the methyl-substituted carbon. Since it is a tertiary position, the positive charge can be stabilized by the electron-donating inductive effect of the methyl group.