第九章_亲电加成反应-试卷资料.ppt

* 1.3 烯烃亲电加成反应的活性 1. 烯烃结构对加成速率的影响 * 不发生亲电取代反应，发生亲核取代反应！ * 2. 亲电试剂对加成速率的影响 对于特定烯烃，卤化氢的加成速率与酸性强弱一致 HI HBr HCl HF 对于特定烯烃，混合卤素的加成速率与其异裂难易程度相符 ICl IBr I2 1.4 烯烃亲电加成反应的定向规律 区域选择性影响因素：电子效应，空间效应 1. 电子效应 “Markovnikov 规则”：质子加到含氢较多的双键碳原子上 “围绕碳正离子的?-C?C单键旋转，当带正电荷碳原子的p轨道轴和?-C?H键的?轨道轴在同一平面时，这两个轨道可发生部分重叠，使部分正电荷分散到甲基上，起稳定碳正离子的作用，这种现象称超共轭作用” * 对含强吸电子基团的烯烃与不对称亲电试剂的加成，从表面上看是反马氏规则的。 也适用于苯乙烯类与卤化氢等不对称试剂的加成的区域选择性，且当苯环上连有强吸电子基时，其区域选择性与吸电子基和双键碳原子直接相连时相似。 * 2. 立体效应 * 2 炔烃和丙二烯类的亲电加成反应 2.1 炔烃的亲电加成 Since alkynes have ? type orbitals, it is not surprising that there is a good deal of similarity to the reactivity of alkenes. The fundamental questions about additions to alkynes include the following: How reactive are alkynes in comparison with alkenes? What is the stereochemistry of additions to alkynes? What is the regiochemistry of additions to alkynes? The important role of bridged ions in addition reactions of alkenes raises the question of whether similar species are involved with alkynes, where the ring includes a double bond and bridged intermediates and would be expected to be substantially more strained. * The basic mechansims that are considered to be involved in electrophilic additions to alkynes: Mechanism A involves a discrete vinyl cation. In general, this reaction will lead to a mixture of the two stereoisomeric addition products. vinyl cation syn + anti Mechanisms B and C depict bridged intermediates formed without or with participation of a second electrophilic molecule. They should lead to anti addition. bridged intermediate bridged intermediate AdE3 AdE2 * Mechanism D is a termolecular process that would be expected to be a stereospecific anti addition. AdE3 Reactivity: In general, alkynes are somewhat less reactive than alkenes toward many electrophiles. A major reason for this difference in reactivity is the substantially higer energy of the vinyl cation intermediate that is formed by an electrophilic attack on an alkyne. For additions that proceed through bridged interm