Electophilic Aromatic Substituion - fccjus：亲电芳香取代- fccjus.pptVIP

McMurry Organic Chemistry 6th edition Chapter 16 (c) 2003 16. Chemistry of Benzene: Electrophilic Aromatic Substitution Based on McMurry’s Organic Chemistry, 6th edition, Chapter 16 ?2003 Ronald Kluger Department of Chemistry University of Toronto Substitution Reactions of Benzene and Its Derivatives Benzene is aromatic: a cyclic conjugated compound with 6 ? electrons Reactions of benzene lead to the retention of the aromatic core Electrophilic aromatic substitution replaces a proton on benzene with another electrophile 16.1 Bromination of Aromatic Rings Benzene’s ? electrons participate as a Lewis base in reactions with Lewis acids The product is formed by loss of a proton, which is replaced by bromine FeBr3 is added as a catalyst to polarize the bromine reagent Addition Intermediate in Bromination The addition of bromine occurs in two steps In the first step the ? electrons act as a nucleophile toward Br2 (in a complex with FeBr3) This forms a cationic addition intermediate from benzene and a bromine cation The intermediate is not aromatic and therefore high in energy (see Figure 16.2) Formation of Product from Intermediate The cationic addition intermediate transfers a proton to FeBr4- (from Br- and FeBr3) This restores aromaticity (in contrast with addition in alkenes) 16.2 Other Aromatic Substitutions The reaction with bromine involves a mechanism that is similar to many other reactions of benzene with electrophiles The cationic intermediate was first proposed by G. W. Wheland of the University of Chicago and is often called the Wheland intermediate Aromatic Chlorination and Iodination Chlorine and iodine (but not fluorine, which is too reactive) can produce aromatic substitution with the addition of other reagents to promote the reaction Chlorination requires FeCl3 Iodine must be oxidized to form a more powerful I+ species (with Cu+ or peroxide) Aromatic Nitration The combination of nitric acid and sulfuric acid produces NO2+ (nitronium ion) The react