yqChapter 16 Ketones and Aldehydes I3.pptVIP

Friedel-Crafts acylation Acyl chloride/AlCl3 + benzene ? Aryl ketone CO + HCl + AlCl3/CuCl + benzene ? benzaldehyde (Gatterman-Koch) Hydration of terminal alkyne Use HgSO4, H2SO4, H2O for methyl ketone Use Sia2BH followed by H2O2 in NaOH for aldehyde. Synthesis from Acyl Chlorides Use lithium dialkylcuprate (R2CuLi), formed by the reaction of 2 moles of R-Li with cuprous iodide. Use a mild reducing agent to prevent reduction to primary alcohol. Ketones from Nitriles A Grignard or organolithium reagent attacks the nitrile carbon. The imine salt is then hydrolyzed to form a ketone. ArC?N ?-C10H7MgBr n H2O n H2O H+ n HCl SnCl2 ArCH=NH H2O ArCH=O SnCl2/HCl H2O Homework Pg758 16.24 (b)(g)(h)(i)(l)(m)(p) 16.29 (b)(d) 16.31, 16.35, 16.43 * 反应中使用弱酸催化剂,一般pH = 5-6。若使用酸性太强的酸，会把亲核的氨基变为不活泼的铵离子，而不利于反应的进行。 Application anhydrous acid，dry HCl gas? Water! How to remove? (2) ROH Acetals as Protecting Groups 形成缩醛或缩酮在合成中的应用： 保护羟基 2,3-二氢-4H吡喃 法沃斯基重排 (3) RSH Addition of Sulfur Nucleophiles Synthesis Using 1,3-Dithiane Remove H+ with n-butyllithium. Alkylate with primary alkyl halide, then hydrolyze. (4) NaHSO3 Yields white precipitates，which can dissolve in H2O purifying products! Identifying Aldehydes and Ketones 2. Nucleophile reagents containing N RNH2 and YNH2 经历亲核加成和脱水两个步骤。 可逆，经酸水解可得回醛酮。 (亚胺) Aldehydes and ketones react with a primary amine to form an imine This is a nucleophilic addition–elimination reaction The pH of the reaction must be controlled pH = 5-6! Why? Hydrazone: Wolff-Kishner Reduction: strongly basic media Clemmensen Reduction: strongly acid media The reduction of thioacetals: neutral solution The Wolff-Kishner Reduction 保护羰基 ?生成的含碳氮双键的化合物有顺反异构： E型 Z型 ?几乎所有的醛和酮都可以与氨的衍生物加成 ?产物，尤其是腙和苯腙一般都是黄色晶体，可用于定性鉴别。故又称氨的衍生物为羰基试剂 *贝克曼重排 *酮肟在酸性催化剂的作用下重排成酰胺的反应称为贝克曼重排。 + NH2OH H+ R’-C-NHR O = 水解 R’-C-OH + RNH2 = O PCl5, H2SO4, POCl3, HCl, 乙酸-乙酸酐 通常以E构型为主。 * 贝克曼重排反应的特点 （1）重排反应是在酸催化下完成的。 （2）只有处于羟基反位的烃基才能迁移。 （3）基团的迁移和羟基离去是同步的。 （4）迁移基团在迁移过程中构型保持不变。 H2SO4 乙醚