缩合反应课件.pptxVIP

会计学; 碱催化机理:;第3页/共139页;甲醛与含有a-活泼氢的醛、酮之间的缩合;催化剂的影响 以碱催化剂为主，酸催化剂应用较少 ④应用特点 定向醇、醛缩合 (a) 烯醇盐法 ;;（2）芳醛与a-活性氢的醛、酮的缩合;应用特点 制备反式芳丙醛;有机小分子脯氨酸催化 直接 Aldol 反应;第10页/共139页;（3）分子内的羟醛缩合;Robinson环化;第13页/共139页;第14页/共139页;第15页/共139页;第16页/共139页;2. 不饱和烃的a羟烷基化（Prins反应）;;Mechanism;第20页/共139页;第21页/共139页;3. 安息香缩合;第23页/共139???;影响因素 ① 芳醛结构的影响 强吸电子、强供电子对反应都不利； 自身缩合、交叉缩合;② 催化剂的影响 NaCN剧毒，可用噻唑鎓盐、咪唑鎓盐等代替;第26页/共139页;第27页/共139页;Example;第29页/共139页; 4.有机金属化合物的a-羟烷基化;第31页/共139页;metal: Zn, Mg, Cd, Ba, In, Ge, Co, Ni, Ce; metal salt: SmI2, CrCl2, TiCl2, CeX3, Na2Te, R3SnLi, R3Sb/I2, Et2AlCl;most often ether solvents are used such as diethyl ether,tetrahydrofuran, 1,4-dioxane and dimethoxyethane, but mixtures of these solvents with aromatic hydrocarbons and more polar solvents such as acetonitrile, dimethyl formamide, dimethyl sulphoxide, and hexamethylphosphoric triamide are also used;;第34页/共139页;催化剂; 例如:;（2）Grignard反应;第38页/共139页;第39页/共139页; 机理:;;③影响因素 1) the reagents are predominantly prepared by reacting alkyl, aryl, or vinyl halides with magnesium metal in aprotic nucleophilic solvents (e.g., ethers, tertiary amines); 2) the reagents are usually thermodynamically stable but air and moisture sensitive and incompatible with acidic functional groups (e.g., alcohols, thiols, phenols, carboxylic acids, 1°, 2° amines, terminal alkynes);;二、 a-卤烷基化反应(Blanc反应); 3.影响因素 也可用ZnCl2(干)等Lewis酸。苯环上供电子基,有利于反应进行。吸电子基不利于反应进行。; 引入-CH2Cl后，可进一步转化成其他官能团并增长碳链。;三、a-氨烷基化反应 ;反应机理;第48页/共139页; 如：;Introduction;1. Metal Catalysis 2. Proline Catalysis 3. Br?nsted Acid-Catalysis 4. Protonated Chiral Catalysis 5. ACDC 6. H-Bond Catalysis 7. PTC ;;Proline catalysis;Br?nsted acid-catalysis;4. Protonated Chiral Catalysis ;;H-Bond Catalysis;;2. Pictet-Spengler reaction;第60页/共139页;Baldwin环化规则;Baldwin环化规则 SP3 = tet；SP2 = trig；SP = dig SP3: 5-6- endo 禁阻 SP2: 3-5-endo 禁阻 SP: 3-4- exo 禁阻 其他允许;（3）影响因素 ① only β-arylethylamines with electron-donating substituents afford high yields; ② the reaction is