浙江大学马成有机化学乙课件 Chapter 13.pdfVIP

Chapter 13 Enol and Enolate. Reactions at the α-Carbon of Carbonyl Compounds 2009/9/13 1 Summary • The second site of reactivity of carbonyl : a hydrogen bonded to α-carbon adjacent to the carbonyl carbon (called an α-carbon) is sufficiently acidic to be removed by a base. • Basic concepts: the acidity of hydrogen on α- carbon; tautomer, enol and enolate; the stability of enol and enolate ion • Reactions at the α-carbon of aldehyde and ketone (α-carbon halogenation, α-substitution reaction, the aldol reaction, conjugate addition reactions) • Reactions at the α-carbon of carboxylic acid derivatives (claisen condensation, α-carbon halogenation, active methylene systems) 2009/9/13 2 12.1 Basic Concepts 1. Carbonyl Nucleophilic Attack Aldehydes and Ketones, Addition, as discussed in Chapter 11 Carboxylic Acid Derivatives, Substitution, as discussed in Chapter 12 2009/9/13 3 2. Electrophilic attack at α- Carbon a. The acidity of Hydrogen on α- Carbon (Electronagativity Delocalization) For carbonyl compounds: 2009/9/13 4 b. Tautomerization (Keto tautomer, Enol tautomer and Enolate) • Due to the acidity of Hydrogen on α-Carbon , Keto-Enol is reasonable a) Enol, Keto-tautomer and enolate anion (enol tautomer conjugate base) 2009/9/13 5 b) Resonance contributors of enol and enolate • Enol • Enolate (most important: pay attention to the difference between the ketone enolate and ester enolate resonance contributo