郑州大学有机化学7芳香烃例析.ppt

7.8.3 Fused-ring arenes(稠环芳烃) 菲 萘 蒽 1 2 3 4 5 6 7 8 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 α β γ α β 1-硝基萘 5-甲基-2-萘磺酸 1,6-萘二胺 α-硝基萘 芘 苯并[a]芘 蔻 A fullerene A portion of a nanotube Graphene(石墨烯) is a one-atom-thick planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. It can be visualized as an atomic-scale chicken wire made of carbon atoms and their bonds. Graphene is the basic structural element of some carbon allotropes(同素异形体) including graphite, carbon nanotubes and fullerenes. It can also be considered as an infinitely large aromatic molecule. The Nobel Prize in Physics for 2010 was awarded to Andre Geim and Konstantin Novoselov “for groundbreaking experiments regarding the two-dimensional material graphene”. 化学反应 还原反应 氧化反应 加成反应 亲电取代反应 easier to form more stable 定位规律 萘发生亲电取代时，环上的活化基使取代多发生在同环 活化基在1位时，取代多发生在4位 活化基在2位时，取代多发生在1位，也可能发生在6位(在异环) 钝化基使取代多发生在异环 卤化，硝化多发生在α位(同时考虑位阻效应) 磺化，酰化多发生在β位 蒽作为二烯体与亲二烯体发生D-A反应 萘及其衍生物的合成-Haworth反应 蒽及其衍生物的合成 菲及其衍生物的合成 Are all fully-conjugated, cyclic systems(called annulenes轮烯) aromatic? √ √ 7.9 Hückel’s Rule and Aromaticity (休克尔规则与芳香性) 7.9.1 Hückel’s Rule A molecule is aromatic if it Is cyclic and planar Is completely conjugated Contains 4n+2 π electrons An aromatic compound is more stable than a similar acyclic compound An antiaromatic compound is less stable than a similar acyclic compound Aromaticity (芳香性)(4n+2π电子) Antiaromaticity (反芳香性)(4nπ电子) Nonaromaticity (非芳香性) An nonaromatic compound is comparable in stability to a similar acyclic compound 7.9.2 Nonbenzenoid system(非苯体系) Cyclopropene(环丙烯) 非芳香性 芳香性 反芳香性 Cyclobutadiene(环丁二烯) [4]annulene [4]轮烯 反芳香性 Cyclopentadiene(环戊二烯) 非芳香性 芳香性 理论上反芳香性 芳香性 环戊二烯负离子可与亲电试剂反应 A calicene(杯烯) × Ferrocene (二茂铁)——a “sandwich” 18 π电子 很稳定，具有芳香性，可以发生亲电取代反应 Cycloheptatriene(环庚三烯) 非芳香性 芳香性 理论上反芳香性