南理工有机化学第五章 芳香烃.ppt

第五章 芳烃 芳香性 Suggest a synthesis of propylbenzene, beginning with benzene. Reactions of Aromatic Sidechains (1) Like other useful and popular chemical concepts (chemical bonds, charges, electronegativities, hyperconjugations etc.), aromaticity is non-reductive, and lacks of clear physical bases. (2) Aromaticity is not a physical observable, having no precise experimental definition. (3) Aromaticity is just like to define beauty in our daily life! Easily to recognize (but not always) Many kinds Hard to compare Difficult to quantify Various opinions, no general agreement Interpreted differently (4) Aromaticity is a time-dependent concept, of which new aspects are pending for discovery. (5) Aromaticity is a property associated with extra stability and many other unusual manifestation. 大环芳香体系-具有交替的单双键的结构多烯烃（轮烯）芳香性的判定 1）共平面或接近平面 2）轮内氢原子没有排斥作用 3）∏电子数符合4n+2规则 （1）[10]轮烯 （2） [14] 轮烯 （4）[18] 轮烯 （3）[16] 轮烯 Aromaticity A. Hückel 4n + 2 rule A planar, cyclic, conjugated p system will be aromatic when it has [4n + 2] p electrons (n = 0, 1, 2, 3...). aromatic 6 p electrons 10 p electrons 14 p electrons 4 p electrons 8 p electrons not aromatic A Molecular Orbital Description of Aromaticity and Antiaromaticity Molecular orbitals below the midpoint of the cyclic structure are bonding molecular orbitals, those above the midpoint are antibonding molecular orbitals, and any at the midpoint are nonbonding molecular orbitals. This scheme is sometimes called a Frost device (or a Frost circle) in honor of Arthur A. Frost, an American scientist who devised this simple method. Frost device (or a Frost circle) Notice that the number of Π molecular orbitals is the same as the number of atoms in the ring because each ring atom contributes a p orbital. Aromaticity C. Heterocyclic aromatic compounds hybridizes to sp2 to allow six electrons in p system O contributes two p electrons sp2 orbital N contributes one p electron sp2 orbital perpendicular