[工学]有机化学复习要点2012-2013.pptVIP

9-10 Hydrogenation Alkene + H2 ? Alkane Catalyst required, usually Pt, Pd, or Ni. Finely divided metal, heterogeneous Syn addition Simmons-Smith Best method for preparing cyclopropanes. Epoxide Stereochemistry Since there is no opportunity for rotation around the double-bonded carbons, cis or trans stereochemistry is maintained. 烯烃结构不同,被KMnO4氧化产物也不同,此反应可用于推测原烯烃的结构。 此反应用于烯烃的 结构和碳碳双键的 鉴定。 烯烃结构不同,被臭氧氧化产物也不同,此反应可用于推测原烯烃的结构。 此反应用于烯烃的 结构和碳碳双键的 鉴定。 Ozonolysis Example Homework 9-30,9-37 Acidity Table Qualitative Test定性实验 红棕色沉淀 Reagent is AgNO3 or CuNO3 in alcohol, orammonia is added to form the complex ion. The solid is explosive when dry. Copper tubing is not used with acetylene.  10-6 Alkynes from Acetylides Acetylide ions are good nucleophiles.（乙炔离子是好的亲核试剂。） SN2 reaction with 1? alkyl halides（伯卤代烃） lengthens the alkyne chain. Reagents for Elimination 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. （氨基钠，在150?，其次是水，有利于终端炔烃生成） Lindlar’s Catalyst Powdered BaSO4 coated with Pd, poisoned with quinoline. H2 adds syn, so cis-alkene is formed. Hydration of Alkynes（炔烃的水化作用） Mercuric sulfate in aqueous sulfuric acid adds H-OH to one pi bond with a Markovnikov orientation, forming a vinyl alcohol (enol) that rearranges to a ketone.（硫酸汞硫酸溶液中添加一个h-oh丕债券与马氏规则方向，形成一个乙烯醇（烯），重新排列，酮。） Hydroboration-oxidation adds H-OH with an anti-Markovnikov orientation, and rearranges to an aldehyde. （ 氧化硼氢化反应 加h-oh与反马氏定位，并重新安排一个醛。 ） Hydroboration - Oxidation B and H add across the triple bond. Oxidation with basic H2O2 gives the enol. Homework 10-9,10-21,10-26， Relative Stabilities twice 1-pentene more substituted 烯丙型 3° 2° 1° 乙烯型 烯丙基 碳正离子的稳定性： Diels-Alder Reaction Otto Diels, Kurt Alder; Nobel prize, 1950 Produces cyclohexene ring Diene + alkene or alkyne with electron-withdrawing group (dienophile) 反应特点： 可逆反应 双烯体：供电基；亲双烯体：吸电基 亲双烯体： 吸电子取