清华大学有机化学李艳梅老师chapteralcoholandphenolfinal.pptx

1;醇（Alcohol）;Content;Part II Phenol/Hydroxybenzene 10.7 Structure and nomenclature 10.8 Physical and spectroscopic properties 10.9 Chemical reactions 10.10 Preparations 10.11 Sources and usages ;Part I Alcohols 第一部分 醇 ; ;;异构;分类;命名;第10页/共82页;Inter molecular hydrogen bond;Simple alcohols may form co-crystals with inorganic salts. 低级醇与一些无机盐（如：MgCl2、CaCl2、CuSO4等）形成结晶状的分子化合物 － 结晶醇（醇化物）;;ν(O-H);ν(-OH);ν(O-H);NMR; ;Lone pair electrons Basicity Nucleophile;OH is not a good leaving group. Proton is often required to change the bad leaving group OH into a good leaving group OH2+;酸、碱性;;;Na;(B) Basicity 碱性; 酯化反应;Acyl chloride;Mechanism 机理;第29页/共82页;第30页/共82页;亲核取代反应;(A). Reactions with HX 与HX的反应;SN1 or SN2 ?;易发生重排;Mechanism----neighboring group participation 邻基参与;Lucas reagent: Lucas试剂;(B). Reactions with PXn;(C) Reactions with SOCl2;脱水与消除;Mechanism;(B) Intramolecular dehydration ;Mechanism; Rearrangement occurs when a more stable anion is formed.;氧化反应;第45页/共82页;Sarrett reagent：;When air is pumped in, water vapor is generated.; ; 与一元醇类似的性质;Reactions different from monobasic alcohol 多元醇的特殊性质;(B). Reaction with periodic acid 与高碘酸的反应;Mechanism;注意：环状酯中间体，要求两个羟基处于顺式;Application ;(C). Pinacol rearrangement 嚬哪醇重排;Which carbocation is favored ? 生成哪个碳正离子？;Which group shifts ? 哪个基团迁移？;Shifting group and leaving group 迁移的立体化学要求;(D). Polymerization and cyclization 聚合与成环;10.5 Preparation of alcohol (learn on your own) 10.6 Sources and usages (learn on your own);Part II Phenols 第一部分 酚 ;10.7 Structure and nomenclature 结构和命名;Electron-donating conjugation;10.8 Physical and spectroscopic properties;;Mass spectrometry;第67页/共82页; ; ;白色 极灵敏（10ppm即可显色） 可用于鉴别苯酚;Other properties 苯酚的特殊反应;;(B). Reaction with FeCl3 与FeCl3的反应;(C). Oxidation;10.10 Preparations;苯酚的制备;(B). Hydrolysis of Benzyl Chloride 氯苯水解;(C). Cumene Oxidation 异丙苯氧化; 萘酚的制备;(B). Hydrolysis of α-naphthalidine α-萘胺水解 ;Thank you