01有机合成绪论终.pptVIP

有机合成Organic Synthesis 徐莉lindafeng_xul@126.com 教材与参考书 1、《有机合成》黄培强，靳立人，陈安齐 高等教育出版社 For Ketone: Baeyer-Villiger Reaction (CF3CO3H or CH3CO3H) Note1:LiAlH4和NaBH4属负氢离子还原剂，主要发生亲核反应，对C=O，C=N，S=O，N=O等极性双键进行进攻，而对极性较小的C=C则一般不发生反应，因而具有一定选择还原能力。 特点：条件温和，反应速度快，产率高，选择性好。 LiAlH4—还原能力强，选择性较好。能还原醛酮，羧酸，酯，酰胺，肟，腈，卤代烃，硝基化合物等；在还原α,β-不饱和醛酮时，一般不影响碳碳双键。NaBH4-是一种缓和的还原剂，一般只能使醛、酮、酰氯还原成醇，有时可还原成酸酐。但不还原羧酸、酯、酰胺、腈及硝基化合物等。如： ? Wolff-Kishner reduction ?? Conditions Semicarbazone NaOEt or other strong base, 200℃, sealed tube. ↓ NaOH or KOH, hydrazine hydrate and carbonyl compound, diethylene glycol, 180℃~200℃, reflux. ↓ Hydrazone , KOBut , DMSO , room temperature ----Preparation of Ether---- 1. Williamson Synthesis 2. Alkoxymercuration-Demercuration ----Preparation of Ether---- ----Preparation of Alkylbenzene---- 1. Friedel-Crafts Alkylation 2. Conversion of Side Chain ----Preparation of Alkylbenzene---- ----Preparation of Phenol---- 1. Hydrolysis of Diazonium Salts 2. Alkli Fusion of Sulfonates ----Preparation of Phenol---- ----Preparation of Amine---- 1. Reduction of Nitro Compounds 2. Reaction of Halides with ammonia or Amines 3. Reductive Amination 4. Reduction of Nitriles 5. Hofmann Degradation of Amides ----Preparation of Amine---- ----Reaction of Diazonium---- 1. Replacement of Nitrogen 2. Coupling ----Reaction of Diazonium---- ----Preparation of Aldehyde Ketone---- 1. Oxidation of Alcohols 2. Oxidation of Methylbenzene 3. Reduction of Acid chloride 4. Friedel-Crafts Acylation ----Preparation of Aldehyde Ketone---- CrO3与吡啶生成的络合物(Sarretty试剂)能迅 速将伯醇、仲醇氧化成醛、酮，产率好，而且往往不影响碳碳双键。 吡啶,rt 吡啶,rt Jones试剂（CrO3)溶于H2SO4，可使不饱和的仲醇氧化成相应的酮，烯键不受影响。 新制二氧化锰也是一种选择性氧化剂，能氧化与烯丙基或苄基相连的OH生成醛酮，对β碳上的键无影响 石油醚 4. ----Reactions of Aldehyde Ketone---- 1. Oxidation 2. Reduction 3. Addition of Cyanide 4. Addition Derivatives of ammonia 5. Addition of Alcohols 6. Cannizzaro Reaction 7. Addition of Grignard Reagent ----Reactions of Aldehyde Ketone---- * 2、《有机合成设计》斯图尔特.