酮和烯醇互变异构体.PPT

Chapter 13 α-Substitution and Condensations of Enols and Enolate Text 1: Chapter 22, p 1003-1056 Text 2: 11,13章 α-Substitution (α-取代) α-halogenation α-alkylation Condensation (缩合) The Aldol reaction (羟醛缩合反应) The Perkin reaction (珀金反应) The ester condenstion (酯缩合反应) Synthesis using β-dicarboyl compounds Conjugate additions (共轭加成): the Michael reaction The Robinson annulation (罗宾逊增环反应) 13.5 The aldol condensation The Malonic ester synthesis:----- Synthesis of substituted acetic acids The Knoevenagel condensation（克诺温格缩合） Assignment Text-1: 22-62, 64, 65, 66, 69, 70, 71, 75, 77 Text-2: 8, 9, 15 13.6 The Claisen ester condensation (克莱森酯缩合) pKa : ~24, less acidic than ketones and aldehydes (pKa~20) 13.6 The Claisen ester condensation (克莱森酯缩合) β-keto ester（ β-酮酸酯） Mechanism of ester condensation 酯缩合机理 Base: NaOC2H5, not NaOCH3，or NaOH, Why? 乙酰乙酸乙酯 Self-condensation, 自缩合 The Dieckmann condensation ——a Claisen cyclization Crossed Claisen condensations 交叉克莱森缩合 Crossed Claisen condensation between ketones and esters β-keto ester（ β-酮酸酯） diketo ester（ 二酮酸酯） β-diketone（ β-二酮） 13.7 Synthesis using β-carbonyl compounds(β-二羰基化合物在合成中的应用) pKa1: 13 11 丙二酸二乙酯 乙酰乙酸乙酯 15.7(H2O ) 16(EtOH) mono- substituted acetic acids 单取代乙酸 Decarboxylation (脱羧) Decarboxylation (脱羧) di- substituted acetic acids 二取代乙酸 Problem: target molecule: Temporary ester group The acetoacetic ester synthesis: -----Synthesis of substituted acetones Temporary ester group For example: The target molecule: 酮式分解 酸式分解 Why? Problem: target molecule: Problem: target molecule: Summary Temporary ester group 13.8 Michael Addition: conjugate addition (麦克尔加成, 共轭加成） 1,2-addition 1,4-addition Michael addition Michael acceptor 麦克尔受体 Michael donor 麦克尔给体 * 13.1 Enols and enolate ions （烯醇和烯醇负离子） Enol form (烯醇式，unstable) Resonance-stabilized anion 烯醇阴离子，Enolate ion Keto form (酮式，Stable) Keto form (酮式， Stable) Enol form (烯醇式， unstable) Resonance-stabil