第4章 消除反应.ppt

逆Cope消除： （2）酯的裂解： （3）b-乙酰氧基酯在碱性条件下消除： J. Org. Chem. 2007, 72, 793-798 （4）亚砜和硒氧化物的消除 （6）邻二卤代烃在DMSO作用下消除： J. Org. Chem. 2007, 72, 6016-6021 4.5 E1 和 E2的竞争 Strong base is needed for E2 but not for E1 E2 is stereospecifc, E1 is not E1 gives Zaitsev orientation 底物结构的影响 4.6 消除与取代之竞争 Steric bulk favors elimination We already saw that SN2 substitution on a tertiary carbon is not possible, therefore E2 elimination will prevail (beside E1 elimination) 碱性与亲核性的影响 There is a strong similarity between the E2 and SN2 reactions: strong nucleophiles favor substitution, while strong bases favor elimination Summary of Reactivity: SN1, SN2, E1, E2 * * * * * * 第4章 消除反应 Chapter 4 Elimination Reactions 4.1 E1消除 4.2 E2消除 4.3 E1CB消除 4.4 Ei消除 4.5 E1和E2之竞争 4.6 消除和取代之竞争 a-消除 vs b-消除 a-消除: b-消除: a b 消除和取代总是在竞争？ 消除反应的区域选择性——Zaitsev消除 和 Hofmann消除 Saytzeff vs Hofmann elimination Saytzeff 烯烃 Hofmann 烯烃 碱体积越大，越有利于Hofmann烯烃的生成！ Effect of the leaving group Especially quarternary ammonium leaving groups favor the Hofmann product The three eliminations E1cB: the proton is removed first, an anion is formed E1: the leaving group departs first, a cation is formed E2: all processes occur at the same time E1 机理： 决速步 4.1 E1消除 反应动力学： V = k [RX] E1反应与SN1反应竞争—— 碱性增强，消除产物增多！ 区域选择性：Zaitsev规则 为何生成Zaitsev烯烃？ E2机理： 4.2 E2 消除 反应动力学：V=k[R-X][B] 4.2.1 Zaitsev消除 Kinetic Isotope Effect Substitute deuterium for hydrogen at ? position Effect on rate is kinetic isotope effect (kH/kD = deuterium isotope effect) Rate is reduced in E2 reaction Heavier isotope bond is slower to break Shows C-H bond is broken in rate-limiting step 底物结构对反应速度的影响： Relative reactivity: R3CX R2CHX RCH2X trans: cis = 6:1 ——Antiperiplanar allows orbital overlap and minimizes steric interactions 立体化学：反式共平面 Elimination From Cyclohexanes 4.2.2 Hofmann 消除： ——季铵碱热解成烯烃、叔胺和水的反应 区域选择性：Hofmann 规则 对Hofmann 消除的解释： 例外： * 4.3 E1cB消除 * E1cB Reaction With an acidic proton; E1cB Biological Elimination: With a poor leaving group; More exampl