郑州大学 有机化学6炔烃 二烯烃.ppt

enediyne antibiotic (烯二炔抗生素);Chapter 6 Alkynes and Dienes;Electronegativity(电负性)：CspCsp2Csp3;IUPAC names;(Z)-3,6-庚二烯-1-炔 (Z)-3,6-heptadien-1-yne;4-乙烯基-1-庚烯-5-炔 4-vinyl-1-hepten-5-yne;6.3.1 Acidity of terminal alkynes (末端炔烃的酸性);(stronger acid) (stronger base);RC≡C–H + R’MgX ;Addition to carbony compounds (与羰基化合物的加成);Halogenation of terminal alkynes(末端炔烃的卤代);6.3.2 Reduction of alkynes (炔烃的还原);Reduction with Na or Li in liquid NH3 (用金属钠或金属锂在液氨中还原);Reduction with LiAlH4 (用氢化铝锂还原);6.3.3 Hydroboration (硼氢化反应) ;6.3.4 Electrophilic addition (亲电加成) ;Addition with HX(与卤化氢加成);Reactivity of alkynes (炔的活性): RC≡CR’ RC≡CH HC≡CH;Addition with X2(与卤素加成);Addition with H2O (与水加成);6.3.5 Oxidation of alkynes (炔烃的氧化);;6.4 Preparation of alkynes (炔烃的制备);6.4.1 Dehydrohalogenation of dihalides (二卤代物脱卤化氢);Molten KOH or alcoholic KOH at 200?C favors an internal alkyne. Sodium amide, NaNH2, at 150?C, followed by water, favors a terminal alkyne. (熔融的氢氧化钾或者氢氧化钾醇溶液常使炔键移向链中，而氨基钠使炔键移向链端);6.4.2 Alkylation of metal alkynide (金属炔化物的烷基化);E2;Retrosynthetic Analysis (逆合成分析) ;Protects against: Strokes (中风) coronary thrombosis (冠状动脉血栓) hardening of the arteries (动脉硬化);Conjugated dienes(共轭二烯烃);1,3-Cyclohexadiene ;6.5 Structure and Physical Properties of Conjugated Dienes (共轭二烯的结构和物理性质);6.5.1 π,π-conjugation (π,π-共轭);6.5.2 The molecular orbital theory (分子轨道理论);;Highest Occupied Molecular Orbital 最高占有轨道;The overall energy of the two bonding butadiene molecular orbitals is lower than that of the two molecular orbitals for ethene. This means that butadiene is more thermodynamically stable than we might expect if its structure were just two isolated double bonds (丁二烯两个成键分子轨道的总能量低于两个乙烯分子轨道的能量。这意味着丁二烯在热力学上比两个孤立的双键稳定) The HOMO for butadiene is higher in energy relative to the HOMO for ethene. This means butadiene should be more reactive than ethene towards electrophiles (丁二烯的最高占有轨道的能量比乙烯高。这意味着丁二烯比乙烯更易与亲电试剂反应) The LUMO for butadiene is lower in energy than the LUMO for ethene. Consequently, butadiene w