有机合成绪论(终)优秀培训书.pptVIP

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 c) Reduction with borane and dialkylboranes NaBH4, a nucleophile, adds to the more positive end of a polarized multiple bond. BH3, a lewis acid, attacks electron-rich centers. Reductions of borane do not simply parallel those with NaBH4. ?? 9-Borabicyclo[3,3,1]nonane (9-BBN) It is highly selective for reduction of α,β-unsaturated carbonyl compounds to allylic alcohols. Nitro and ester groups react only slowly. Example: 在有机合成中利用此性质保护羰基(官能团的保护) 实例 ----Reaction of Carbanion---- 1. Halogenation of ketones 2. Nucleophilic Additon to Carbonyl Compounds 3.Claisen and Dieckmann Condensation Reactions ----Reaction of Carbanion---- 机理 Claisen-Schmidt Condensation Reactions c)Knoevenagel reaction d)Benzoin Condensation Reaction e) The Mannich Reaction The Mannich Reaction The Mannich Reaction f)Darzens Reaction 3. Claisen and Dieckmann Condensation Reactions ----Substitution on Aromatic Ring---- 1. Nitration 2. Sulfonation 3. Halogenation 4. Friedel-Crafts Alkylation 5. Friedel-Crafts Acylation 6. Protonation ----Substitution on Aromatic Ring---- ----Preparation of Acid---- 1. Oxidation of Primary Alcohols 2. Oxidation of Alkylbenzene 3. Carbonation of Grignard Reagent 4. Hydrolysis of Nitriles ----Preparation of Acid---- ----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 o