Aromatic Electrophilic Substitution Reactions of Ethers

The alkoxy group (-OR) on an aromatic ether is, like a phenol's -OH, an activating and ortho/para-directing substituent, so aromatic ethers such as anisole undergo electrophilic aromatic substitution readily. HALOGENATION: anisole brominates with Br2 in acetic acid even without a catalyst, giving p-bromoanisole as the major product (with some ortho isomer). NITRATION: anisole with concentrated H2SO4/concentrated HNO3 gives a mixture of ortho- and para-nitroanisole. FRIEDEL-CRAFTS REACTION: anisole, with anhydrous AlCl3 as catalyst, undergoes Friedel-Crafts acylation with acetyl chloride to give predominantly 4-methoxyacetophenone (with some 2-methoxyacetophenone), and Friedel-Crafts alkylation with methyl chloride to give predominantly 4-methoxytolu …