有机化学Chapter 3. Alkenes 烯烃.ppt

(1) 卤化反应 烯烃与卤素在高温下发生α –卤代反应： 这是自由基反应 反应机理： 链引发 链传递 反应条件：h 或 ROOR 使用一些试剂，可在温和的条件下进行 α –卤代反应。 环己烯 NBS 3–溴环己烯 丁二酰亚胺 N–溴代丁二酰亚胺(NBS) ν Additional problems: 1.Vinylcyclopropane reacts with HBr to yield a rearranged alkyl bromide.Follow the flow of electrons as represented by the curve arrows, show the structure of the intermediate in brackets, and show the structure of the final product. 2. Predict the products of the following reactions. Don’t worry about the size of the molecule, concentrate on the functional groups. Cholesterol ( 胆固醇) 作业：Prof. Zhang’s bookPg 114-119, 一、二、三、四、六、七、九、十、十二、十四、十五、十六 (1，3，5)、十八、十九、二十、二十一、二十二、二十三、二十五。 * KMnO4: potassium permanganate * p16 The Structure and Stability of Carbocation The trivalent carbon is sp2-hybridized and has a vacant p orbital extending perpendicular to the plane of the carbon and three attached groups. σ- p σ- p σ-π The Structure and Stability of Carbon Radical Regioselectivity (区域选择 性) of the reaction The reaction that can proceed in more than one direction, but actually in which one direction is preferred. Regiospecific (区域专一的) A more highly substituted carbocation is more stable than a less highly substituted one. + δ + δ + The electron-donating or electron- withdraw effect of a group that is transmitted through σbond. Inductive effect(诱导效应) of substituents: Explanation for “Markovnikov’s rule” (I) (II) The stabilities of carbocation: (I) (II) Electrophilic addition to an unsymmetri- cally substituted alkene give the more highly substituted carbocation. Carbocation Rearrangements (重排) (40%) (60%) HCl Cl- (I) (II) Cl- Stabilities of C+: Tertiary Secondary Hydride-shift 0℃ Problem: Propose a mechanism to account for the following result: Reactivity: HI HBr HCl HF Based on the ability to proton-donating of HX Alkenes? Peroxide effect (过氧化物效应) An unsymmetric alkene reacts with HBr in the