有机化学第十章汇总课件

Chapter 10Chapter 10Alcohols and phenols第十章第十章 醇与酚醇与酚Organic Chemistry A(1)By Prof.Li Yan-MeiTsinghua UniversityChapter 10Alcohols and phenols醇（Alcohol）酚（Phenol）醇（Alcohol）酚（Phenol）ContentContent Part I Alcohols 10.1 Structure,isomerization,classification and nomenclature 10.2 Physical and spectroscopic properties 10.3 Monobasic/Monohydroxyl alcohol 10.4 Polybasic alcohol 10.5 Preparation of alcohol 10.6 Sources and usagesContent Part I AlcoholsPart 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 usagesPart II Phenol/HydroxybenzenePart IAlcohols第一部分第一部分 醇醇Part I 10.1.1 Structure 10.1.2 Isomerization 10.1.3 Classification 10.1.4 Nomenclature 10.1 Structure,isomerization,classification and nomenclature 10.1.1 Structure 10.1 Stru108.5osp3 hybridization 2DVery close to waterMany alcohols completely miscible with water 10.1.1 Structure 结构结构108.5osp3 hybridization 2DV10.1.2 Isomerization 异构异构Position isomerizationFuctional group isomerizationCarbon chain isomerization位置异构位置异构碳架异构碳架异构官能团异构官能团异构10.1.2 Isomerization 异构Posi10.1.3 Classification 分类分类 C12p 根据羟基数目：一元醇 二元醇 三元醇p 根据所连的碳原子不同：一级醇（伯醇）二级醇（仲醇）三级醇（叔醇）p 根据所含碳原子数目：低级醇 中级醇 高级醇10.1.3 Classification 分类 R2CHOH R3COHApplicationsDeal with such metals with alcohol,reducing reaction rate,avoiding explosion.Alcoholic metals are good nucleophiles.醇金属可作为好的亲核试剂醇金属可作为好的亲核试剂。Na(2)Reaction with metals 与(B)Basicity 碱性碱性Boron trifluoride好的离去基团好的离去基团(B)Basicity 碱性Boron triflu 10.3.2 Esterification 酯化反应酯化反应Organic acidInorganic acid某酸某酯某酸某酯硝酸某酯硝酸某酯亚硝酸某酯亚硝酸某酯硫酸氢某酯硫酸氢某酯 10.3.2 Esterification 酯化反应OAcyl chlorideAnhydrideAcyl chlorideAnhydrideMechanism 机理机理Mechanism 机理有机化学第十章汇总课件有机化学第十章汇总课件 10.3.3 Nucleophilic substitution 亲核取代反应亲核取代反应Nucleophilic reagent 亲核试剂亲核试剂HX,PX3,SOCl2.常见产物：常见产物：RX（RCl）10.3.3 Nucleophilic substitu(A).Reactions with HX 与与HX的反应的反应ReactivityMechanism：H+及及ZnCl2的作用的作用-形形成好的离去基团成好的离去基团(A).Reactions with HX 与HXSN1 or SN2?Generally,1o ROH follows SN2 mechanism,while 2o and 3o ROH follows SN1 mechanism,which is often coupled with an anion rearrangement.SN1 or SN2?Generally,1o ROH 易发生重排易发生重排Mechanism-neighboring group participation 邻基邻基参与参与Mechanism-neighboring groupLucas reagent:Lucas试剂试剂Reactivity 反应性反应性Reaction occurs immediately立刻反应立刻反应Reaction occurs after 25 min 片刻片刻(2-5分钟分钟)后反应后反应Reaction occurs when heated 加热才反应加热才反应C6以下一元醇以下一元醇 溶于溶于HCl 不溶于不溶于HCl 变浑变浑 由于鉴别由于鉴别1 10 0、2 20 0、3 30 0醇醇Lucas reagent:Lucas试剂Reacti(B).Reactions with PXnReactionMechanismRCl is often prepared with PCl5 and the corresponding alcohol,while RI with P,iodine,and the corresponding alcohol.不重排不重排(B).Reactions with PXnReactio(C)Reactions with SOCl2No rearrangement!不重排不重排(C)Reactions with SOCl2No re10.3.4 Dehydration and elimination 脱水与消除脱水与消除(A)Intermolecular 分子间脱水分子间脱水 ExampleA side reaction of alcohol dehydration to form ethene.You have performed this experiment at high school.10.3.4 Dehydration and eliminMechanism本质：亲核取代反应本质：亲核取代反应Mechanism本质：亲核取代反应(B)Intramolecular dehydration ExampleThis reaction follows an E1 elimination mechanism.(B)Intramolecular dehydratioMechanismReactivityProductu Follows Zaitzevs ruleu E form本质：消去反应本质：消去反应MechanismReactivityProduct Fou Rearrangement occurs when a more stable anion is formed.注意：注意：u Competition between intermolecular and intramolecular reaction often exists.Under high temperature,elimination is favored,otherwise intramolecular dehydration.Rearrangement occurs when a 10.3.5 Oxidation 氧化反应氧化反应O:Na2Cr2O7,HNO3,KMnO4一般地：10.3.5 Oxidation 氧化反应O:有机化学第十章汇总课件Sarrett reagent：CrO3+pyridine特殊情况：实验室常用方法：实验室常用方法：Jones reagent：CrO3+diluted H2SO4橙色透明橙色透明蓝绿色蓝绿色不透明不透明鉴别！鉴别！pyridinium chlorochromate:氯铬酸吡啶盐氯铬酸吡啶盐（PCC）Sarrett reagent：CrO3+pyridinWhen air is pumped in,water vapor is generated.工业上常用方法：脱氢工业上常用方法：脱氢还原性气氛，还原性气氛，易将产物又还易将产物又还原为醇原为醇When air is pumped in,water v 10.4.1 Reactions similar to monobasic alcohol 10.4.2 Reactions different from monobasic alcohol10.4 Polybasic alcohol 多元醇多元醇 10.4.1 Reactions similar to10.4.1 Reactions similar to monobasic alcohol 与一元醇类似的性质与一元醇类似的性质Acid-base reactionEsterifyingNucleophilic substitutionDehydration and eliminationHydrogenation(Oxidation)Dehydrogenation10.4.1 Reactions similar to m10.4.2 Reactions different from monobasic alcohol 多元醇的特殊性质多元醇的特殊性质(A).Reaction with Cu(OH)2uIdentification of 1,2-diol,or some substance with similar substructure.用于鉴别用于鉴别1,2-1,2-二醇或具有邻二羟基的多元醇二醇或具有邻二羟基的多元醇Soluble,blue蓝色蓝色 可溶可溶10.4.2 Reactions different fr(B).Reaction with periodic acid 与高碘与高碘酸的反应酸的反应ReactionThis reaction is usually used to identify structures.(B).Reaction with periodic acMechanism环状酯中间体环状酯中间体氧化值：氧化值：7氧化值：氧化值：5Mechanism环状酯中间体氧化值：7氧化值：5注意：环状酯中间体，要求两个羟基处于顺式注意：环状酯中间体，要求两个羟基处于顺式均难发生反应均难发生反应注意：环状酯中间体，要求两个羟基处于顺式均难发生反应Application p反应定量进行，由消耗的高碘酸的量可测定邻二醇的量反应定量进行，由消耗的高碘酸的量可测定邻二醇的量p推断结构：推断结构：Application 反应定量进行，由消耗的高碘酸的量可测(C).Pinacol rearrangement 嚬哪醇重排嚬哪醇重排Pinacol嚬哪醇嚬哪醇Pinacolone嚬哪酮嚬哪酮邻二醇在酸作用下邻二醇在酸作用下的重排的重排较不稳定的碳较不稳定的碳正离子（碳外正离子（碳外层层6个电子）个电子）较稳定的较稳定的 盐（碳外层盐（碳外层8个电子）个电子）钅钅 羊羊甲基迁移甲基迁移(C).Pinacol rearrangement 嚬Which carbocation is favored?生成哪个碳正离子？生成哪个碳正离子？主产物主产物次产物次产物Which carbocation is favored?Which group shifts?哪个基团迁移？哪个基团迁移？甲基迁移甲基迁移苯基迁移苯基迁移迁移能力：迁移能力：R-ph ph NO2-ph R CH3 H即：提供电子、稳定正电荷能即：提供电子、稳定正电荷能 力较强的基团优先迁移力较强的基团优先迁移Which group shifts?哪个基团迁移？甲Shifting group and leaving group 迁移的立体化学要求迁移的立体化学要求迁移基团与离去基团迁移基团与离去基团处于反式位置时较易处于反式位置时较易迁移迁移Shifting group and leaving gro(D).Polymerization and cyclization 聚合聚合与成环与成环聚乙二醇聚乙二醇(D).Polymerization and cycliz10.5 Preparation of alcohol (learn on your own)10.6 Sources and usages (learn on your own)10.5 Preparation of alcoholPart IIPhenols第一部分第一部分 酚酚Part II10.7 Structure and nomenclature 结构和命名结构和命名Phenol酚酚Alcohol醇醇10.7 Structure and nomenclatuElectron-donating conjugation=1.6 D强给电子基团强给电子基团Nomenclature 命名命名采用芳烃命名原则。采用芳烃命名原则。Electron-donating conjugation10.8 Physical and spectroscopic properties10.8.1 Physical propertiesp苯酚在冷水中微溶，加热时可无限溶解苯酚在冷水中微溶，加热时可无限溶解p分子间氢键分子间氢键p纯的酚无色，但易被空气中的氧气氧化而呈纯的酚无色，但易被空气中的氧气氧化而呈略红或褐色略红或褐色p毒性毒性10.8 Physical and spectroscop10.8.1 spectroscopic data IR(O-H)(C-O)3610cm-11200cm-1NMR4-12 ppm10.8.1 spectroscopic data IRMass spectrometryMass spectrometry有机化学第十章汇总课件 10.9.1 Electrophilic reactions 10.9.2 Other properties10.9 Chemical reactions 10.9.1 Electrophilic reacti 10.9.1 Electrophilic reactions邻对位活化基邻对位活化基反应条件温和反应条件温和反应速度快反应速度快产物邻、对位为产物邻、对位为主主容易发生多取代容易发生多取代 10.9.1 Electrophilic reactio白色极灵敏（10ppm即可显色）可用于鉴别苯酚控制条件才可获得一卤代产物白色控制条件才可获得一卤代产物10.9.2 Other properties 苯酚的特殊反应苯酚的特殊反应(A).Acidity 酸性酸性1015.74H2OC2H5OH15.9H2CO3C2H225NH334若芳香基团上有吸电子基团，则酚酸性增强。若芳香基团上有吸电子基团，则酚酸性增强。10.9.2 Other properties 苯酚的亲核试剂可用于制备醚可用于制备苯甲醚亲核试剂可用于制备醚可用于制备苯甲醚(B).Reaction with FeCl3 与与FeCl3的反应的反应适用：苯酚，萘酚及其衍生物适用：苯酚，萘酚及其衍生物用途：鉴别苯酚用途：鉴别苯酚 （鉴别具有烯醇结构的化合物）（鉴别具有烯醇结构的化合物）颜色：蓝色，紫色为主颜色：蓝色，紫色为主紫色紫色烯醇结构(B).Reaction with FeCl3 (C).Oxidation对苯醌对位取代基可能脱去注意：注意：1 1、因所用氧化剂通常都有颜色，反应前后颜色变化不明显，故一般不用于鉴别、因所用氧化剂通常都有颜色，反应前后颜色变化不明显，故一般不用于鉴别 2 2、磺化、硝化等反应时应注意反应条件，以免被氧化、磺化、硝化等反应时应注意反应条件，以免被氧化(C).Oxidation对苯醌对位取代基可能脱去注意：110.10 Preparations 10.10.1 Preparations of phenol 苯酚的制备苯酚的制备 10.10.2 Preparations of naphthol 萘酚的制备萘酚的制备10.10 Preparations 10.10.1 P10.10.1 Preparations of phenol 苯酚的制备苯酚的制备(A).Alkali Fusion of Sodium Benzene-sulfonate 苯磺酸碱融苯磺酸碱融法法融熔10.10.1 Preparations of pheno(B).Hydrolysis of Benzyl Chloride 氯苯水解氯苯水解氯苯的制备：(B).Hydrolysis of Benzyl Chlo(C).Cumene Oxidation 异丙苯氧化异丙苯氧化两种化工原料两种化工原料两种石化产品两种石化产品(C).Cumene Oxidation 异丙苯氧化10.10.2 Preparations of naphthol 萘酚的制备萘酚的制备(A).Alkali Fusion 碱融法碱融法 融熔融熔10.10.2 Preparations of naphth(B).Hydrolysis of-naphthalidine -萘胺水解萘胺水解 10.11 Sources and usages (Learn on your own)(B).Hydrolysis of-naphthaliThank you!Thank you!Thank you!