Electophilic Aromatic Substituion - Blinn College：亲电芳香取代-宾氏学院.pptVIP

* 16.8 Benzyne Phenol is prepared on an industrial scale by treatment of chlorobenzene with dilute aqueous NaOH at 340°C under high pressure The reaction involves an elimination reaction that gives a triple bond The intermediate is called benzyne * Evidence for Benzyne as an Intermediate Bromobenzene with 14C only at C1 gives substitution product with label scrambled between C1 and C2 Reaction proceeds through a symmetrical intermediate in which C1 and C2 are equivalent— must be benzyne * Structure of Benzyne Benzyne is a highly distorted alkyne The triple bond uses sp2-hybridized carbons, not the usual sp The triple bond has one ? bond formed by p–p overlap and another by weak sp2–sp2 overlap * 16.9 Oxidation of Aromatic Compounds Alkyl side chains can be oxidized to ?CO2H by strong reagents such as KMnO4 and Na2Cr2O7 if they have a C-H next to the ring Converts an alkylbenzene into a benzoic acid, Ar?R ? Ar?CO2H * Bromination of Alkylbenzene Side Chains Reaction of an alkylbenzene with N-bromo-succinimide (NBS) and benzoyl peroxide (radical initiator) introduces Br into the side chain * Mechanism of NBS (Radical) Reaction Abstraction of a benzylic hydrogen atom generates an intermediate benzylic radical Reacts with Br2 to yield product Br· radical cycles back into reaction to carry chain Br2 produced from reaction of HBr with NBS * 16.10 Reduction of Aromatic Compounds Aromatic rings are inert to catalytic hydrogenation under conditions that reduce alkene double bonds Can selectively reduce an alkene double bond in the presence of an aromatic ring Reduction of an aromatic ring requires more powerful reducing conditions (high pressure or rhodium catalysts) * Reduction of Aryl Alkyl Ketones Aromatic ring activates neighboring carbonyl group toward reduction Ketone is converted into an alkylbenzene by catalytic hydrogenation over Pd catalyst * 16.11 Synthesis of Trisubstituted Benzenes These syntheses require planning and consideration of alternative routes