四川大学有机化学第六章.ppt

UIUC 第六章 芳香烃和苯(Aromatic compound and Phenyl) 芳烃：具有芳香性的碳氢化合物。 芳香性：1）具有稳定的环系 2）易于亲电取代，难于亲电加成 分类 第一节 苯的结构 一、苯的Kekule式 1825年，Faraday从照明气中分离得到 1865年，Kekule提出了苯的环状构造式 苯Kekulé式的正确性 合成印证 问题 Kekulé式中有单双键之分，但事实上键长一样 苯并不象烯烃那样发生氧化、亲电加成反应；苯易于发生亲电取代反应 邻二取代苯只有一种 1925年，Robinson建议 二、苯分子结构的价键解释 苯的平面正六边形构型 C：sp2杂化 苯分子中的骨架 苯分子的?键 三、 苯的?分子轨道模型 原子轨道线性组合 苯?分子轨道能级图 苯分子结构特点 平面正六边形构型 高度对称、高度离域?键 环骨架很稳定 四、苯分子结构的共振论解释 Brief Viewpoint Rules for Arrow-Pushing RESONANCE - 1 Whenever a molecule can be represented by two or more structures that differ only in the arrangement of electrons, then line-bond structures are poor representations of the molecule, and there must be resonance. The real molecule is a hybrid of all of these structures and cannot be represented adequately by any of them. Each of the structures contributes to the hybrid. RESONANCE - 2 When these contributing structures are of about the same energy, then resonance is important. If the contributing structures are of markedly different energy, then resonance will be less important. The contribution of each structure to the hybrid depends upon the relative stability of that structure; the more stable structure makes the larger contribution. RESONANCE - 3 The resonance hybrid has a lower potential energy than any of the contributing structures This decrease in energy is called the resonance energy. Resonance energy is large when resonance is important. Rules for Evaluating Resonance Forms - Part 1 The octet rule should be obeyed, if possible. There should be a minimum of charge separation. The formal charges should correspond to the relative electronegativities of the atoms. Avoid formal charges of the same sign on adjacent atoms. Rules for Evaluating Resonance Forms - Part 2 Keep the magnitude of the formal charges as low as possible Avoid multiple formal charges on any one atom. The relative location of the atoms mustnt be changed. The number of the uns