Effects of Substituents on Reactivity and Orientation

The nature of groups already on an aromatic ring affect both the reactivity and orientation of future substitution. We say, therefore, that substituent groups affect both reactivity and orientation in EAS Electron-donating substituents on a benzene ring make the ring react more rapidly than benzene, and are therefore called activating groups. Furthermore, most activating groups cause the location of electrophilic aromatic substitution to be ortho and/or para to the activating group. Therefore, activating groups are orthopara directing groups. Electron-withdrawing substituents on a benzene ring make the ring react less rapidly than benzene, and are therefore called deactivating groups. -- Most deactivating groups cause the location of electrophilic aromatic substitution to be meta to the deactivating group. Therefore, most deactivating groups are meta directors.
Chapter 15 2

 Activating Groups: Ortho-Para Directors

All activating groups are also ortho-para directors The halides are also ortho-para directors but are mildly deactivating The methyl group of toluene is an ortho-para director

Toluene reacts more readily than benzene, we observe the greater reactivity of toluene in several ways: 1) With toluene, milder conditions (lower temp. and lower conc. of the electrophile ) can be used in EAS than with benzene. 2) Under the same conditions toluene reacts faster than benzene. EX: In nitration, toluene reacts 25 times as fast as benzene.

 The methyl group of toluene is an ortho-para director. Example: When we nitrate toluene with nitric and sulfuric acid, we get mononitrotoluenes in the following relative proportions

The same behaviour is observed in halogenation, sulfonation and so forth.

Chapter 15 4

Alkyl groups are not the only activating groups. Others include groups containing oxygen or nitrogen atoms directly bonded to the ring, such as hydroxyl, alkoxyl, amino and amide or ester groups with the nitrogen or oxygen bonded to the benzene ring. Example: The hydroxyl group and the amino group are very powreful activating groups and are also ortho-para directors. Phenol and aniline react with bromine in water to produce products in which both of the ortho positions and the para positions are substituted.

Alkyl groups and atoms with one or more unshared electron pairs directly bonded to the aromatic ring will be ortho-para directors .

 Deactivating Groups: Meta Directors

The nitro group is a very strong deactivating group. Nitrobenzene undergoes nitration at a rate only 10-4 times that of benzene. The nitro group is a meta director. When nitrobenzene is nitrated with nitric acid and sulfuric acids, 93% of the substitution occurs at the meta position.

The carboxyl group (-CO2H), the sulfonic acid group (-SO3H), and the trifluoromethyl group (-CF3) are also deactivating groups; they are also meta directing groups.

Chapter 15

Halo Substitutents: Deactivating Ortho-Para Directors

The chloro and bromo groups are ortho-para directors . However , even though they contain unshared electron pairs, they are deactivating toward electrophilic aromatic substitution because of the electronegative effect of the halogens. Chlorobenzene and bromobenzene, undergo nitration at a rate approximately 30 times slower than benzene. The relative percentages of monosubstituted products that are obtained when chlorobenzene is chlorinated, brominated, nitrated, or sulfonated are shown in the following table.

 Classification of Substituents

Chapter 15

 The following five rules summarize the aforementioned table: 1) Activating substituents are ortho, para directors. 2) Ortho, para directors, except for alkyl, aryl, and vinyl groups, have nonbonding electrons on the atom attached to the aromatic ring. 3) Deactivating substituents are meta directors. 4) Meta directing groups have at least a partial positive charge on the atom that bonds to the ring carbons. 5) Halogens are an exception to the above rules. They are deactivating, but are ortho, para directing groups, and they have nonbonding electrons.

 An activating group activates all positions to the benzene ring even the positions meta to it. It directs ortho and para simply because it activates the ortho and para positions much more than it does to the meta. A deactivating group deactivates all positions in the ring even the positions meta to it. It directs meta simply because it deactivates the ortho and para positions even more than it does to the meta. Then the effect of any group whether activating or deactivating- is strongest at the ortho and para positions.

 Theory of Substituent Effects on Electrophilic Substitution Reactivity: The Effect of Electron-Releasing and ElectronWithdrawing Groups Any factor that increases the energy of the transition state relative to that of the reactants decreases the relative rate of the reaction. It does this because it increases the energy of activation of the reaction. In the same way, any factor that decreases the energy of the transition state relative to that of the reactants lowers the energy of activation and increases the relative rate of the reaction. The rate-determining step in EAS of substituted benzenes is the step that results in the formation of the arenium ion.

Chapter 15

11

 If Q is an electron-releasing group, the reaction occurs faster than the corresponding reaction of benzene. If Q is an electron-withdrawing group, the reaction is slower than that of benzene. It appears, then, that the substituent (Q) must affect the stability of the transition state relative to that of the reactants. Electron-releasing groups apparently make the transition state more stable. Electron-withdrawing groups apparently make the transition state less stable. Since the arenium ion is positively charged, we would expect the following remarks: An electron-releasing group stabilizes the arenium ion and the transition state leading to it. An electron-withdrawing group make the arenium ion less stable, and in a corresponding way it should make the transition state leading to the arenium ion less stable.