[化学]分子重排反应.pptVIP

姓名: 袁洪亮 班级：应用化学07研 学号：0720902008 Molecular Rearrangements Ⅰ Nucleophilic Rearrangement 1 Wagner-Meerwein rearrangement 2 Pinacolic Rearrangement 3 α-ethandione Rearrangement 4 The Dienone-Phenol Rearrangement 5 The Hofmann Rearrangement 6 The Curtius Rearrangement 7 The Lossen Rearrangement 8 The Schmidt Reaction 9 Beckmann Rearrangement Baeyer-Villiger Rearrangement 11 The Arndt-Eistert synthesis 12 Homologation of Aldehydes and Ketones II Electrophilic Rearrangement 1 favorskii Rearrangement 2 Stevens Rearrangement 3 Sommelet Rearrangement 4 Wittig Rearrangement 5 Fries Rearrangement III Radical Rearrangement Ⅳ Other Rearrangement 1 Stieglitz and Related Rearrangement 2 Boron 杢o-Carbon Migrations I Nucleophilic Rearrangement 1 Wagner-Meerwein rearrangement ( Carbon cation rearrangement ) When alcohols are treated with acid ,in many cases,where two or three alkyl or aryl groups are on the βcarbon.some or all of the product is rearranged. Stable cation Stable cation Mechanism: 2 Pinacolic Rearrangement When vic-diols are treated with acid,they can be rearranged to give aldehydes or ketones, this reaction is called～． Mechanism : (1)The stable cation formed superior Phenyl group move first (2)Under HNO2, the amino alcohol rearranges as that of pinacol (3)Mixtures are ofen produced,and which group preferrntially migrates may depend on the reaction conditions as well as on the nature of the substrate. (4)Epoxides can also rearranged to aldehydes or ketones on treatment with certain metallic catalysis. α-Ethandione Rearrangement (Benzil-benzilic acid Rearrangement) Proton shif (1): It can also be applied to aliphatic diketones and toα－keto aldehydes. (2): α-Ethandione with α- hydrogen will proceed condensation (3): If NaOH was replaced by NaOMe or t-BuONa, α-hydroxycarboxyester will be produced Usually, ethyloxy anion acts as a reduction reagent. 4.The Dienone-Phenol Rearrangement Compoun