1、Chapter 10,Alcohols and phenols 第十章 醇与酚,Organic Chemistry A (1) By Prof. Li Yan-Mei Tsinghua University,醇（Alcohol）,酚（Phenol）,Content,Part I Alcohols10.1 Structure, isomerization, classification and nomenclature10.2 Physical and spectroscopic properties10.3 Monobasic/Monohydroxyl alcohol10.4 Polybasi
2、c alcohol10.5 Preparation of alcohol10.6 Sources and usages,Part II Phenol/Hydroxybenzene10.7 Structure and nomenclature10.8 Physical and spectroscopic properties10.9 Chemical reactions10.10 Preparations10.11 Sources and usages,Part IAlcohols 第一部分 醇,10.1.1 Structure10.1.2 Isomerization10.1.3 Classif
3、ication10.1.4 Nomenclature,10.1 Structure, isomerization, classification and nomenclature,sp3 hybridization, 2D,Very close to water Many alcohols completely miscible with water,10.1.1 Structure 结构,10.1.2 Isomerization 异构,位置异构,碳架异构,官能团异构,10.1.3 Classification 分类, C4,C5 C11, C12,根据羟基数目：,一元醇 二元醇 三元醇,根据
4、所连的碳原子不同：,一级醇（伯醇） 二级醇（仲醇） 三级醇（叔醇）,根据所含碳原子数目：,低级醇 中级醇 高级醇,10.1.4 Nomenclature 命名,Inter molecular hydrogen bond,Boiling point,Melting point,Simple alcohols completely miscible with water 与水形成氢键 低级醇一般与水任意混溶,10.2 Physical and spectroscopic properties,10.2.1 Physical properties,分子间氢键导致熔点、沸点较高,Simple alco
5、hols 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）,MgCl2, CuSO4 ,MgCl2 6 CH3OH,CaCl2 4 C2H5OH,CaCl2 4 CH3OH,用途：除去有机溶剂中少量的醇将醇与其它有机物分开 危害：不可用MgCl2、CaCl2、CuSO4等来干燥低级醇,10.2.1 Spectrometry,IR,(O-H),35503450cm-1,(O-H),34003200cm-1,in inter molecular hydroge
6、n bonding systems,(-OH),36003500cm-1,in intra molecular hydrogen bonding systems,(-OH),32003500cm-1,multi molecule cluster,(-OH),34003200cm-1,(O-H),3710cm-1,(O-H),3300cm-1,(O-H),36003450cm-1,IR of OH bond in water molecule,Solid, ice,Crystallized water,Liquid water,NMR,0.5 - 5.5, 3.7,15 - 19,活泼氢,10.
7、3.1 Acidity and basicity10.3.2 Esterifying10.3.3 Nucleophilic substitution10.3.4 Dehydration and elimination,10.3 Monobasic/Monohydroxyl alcohol,Lone pair electronsBasicityNucleophile,AcidityIonizationReacting with alkali metals,Labile beta-hydrogenEliminationOxidationDehydration,Brief introduction,
8、OH is not a good leaving group. Proton is often required to change the bad leaving group OH into a good leaving group OH2+,好的离去基团,10.3.1 Acidity and basicity 酸、碱性,Strongeracidity,Weaker acidity,(1) Relative acidity 酸性顺序,(A) Acidity 酸性,原因：溶剂化效应的影响,More solvation leads to more stable positive ion.,溶剂化
9、效应的影响：,Strongeracidity,Weaker acidity,Inductive effect,Electron cloud pulled,诱导效应的影响：,Na,(2) Reaction with metals 与金属的反应,K,Ca,Mg,Al,Rb,Sr,Ba,Cs,Reaction rate,RCH2OH R2CHOH R3COH,Applications,Deal with such metals with alcohol, reducing reaction rate, avoiding explosion. Alcoholic metals are good nuc
10、leophiles. 醇金属可作为好的亲核试剂。,(B) Basicity 碱性,Boron trifluoride,好的离去基团,好的离去基团,10.3.2 Esterification 酯化反应,Organic acid,Inorganic acid,某酸某酯,硝酸某酯,亚硝酸某酯,硫酸氢某酯,Acyl chloride,Anhydride,Mechanism 机理,10.3.3 Nucleophilic substitution 亲核取代反应,Nucleophilic reagent 亲核试剂,HX, PX3, SOCl2 .,常见产物：RX（RCl）,(A). Reactions wi
11、th HX 与HX的反应,Reactivity,Mechanism：H+及ZnCl2的作用 - 形成好的离去基团,SN1 or SN2 ?,Generally, 1o ROH follows SN2 mechanism, while 2o and 3o ROH follows SN1 mechanism, which is often coupled with an anion rearrangement.,易发生重排,Mechanism-neighboring group participation 邻基参与,Lucas reagent: Lucas试剂,Reactivity 反应性,Rea
12、ction occurs immediately 立刻反应,Reaction occurs after 25 min 片刻(2-5分钟)后反应,Reaction occurs when heated 加热才反应,C6以下一元醇 溶于HCl,不溶于HCl 变浑,由于鉴别10、20、30醇,(B). Reactions with PXn,Reaction,Mechanism,RCl is often prepared with PCl5 and the corresponding alcohol, while RI with P, iodine, and the corresponding alc
13、ohol.,不重排,(C) Reactions with SOCl2,No rearrangement!,不重排,10.3.4 Dehydration and elimination 脱水与消除,(A) Intermolecular 分子间脱水,Example,A side reaction of alcohol dehydration to form ethene. You have performed this experiment at high school.,Mechanism,本质：亲核取代反应,(B) Intramolecular dehydration,Example,This
14、 reaction follows an E1 elimination mechanism.,Mechanism,Reactivity,Product,Follows Zaitzevs ruleE form,本质：消去反应,Rearrangement occurs when a more stable anion is formed.,注意：,Competition between intermolecular and intramolecular reaction often exists. Under high temperature, elimination is favored, ot
15、herwise intramolecular dehydration.,10.3.5 Oxidation 氧化反应,O: Na2Cr2O7, HNO3, KMnO4,一般地：,Sarrett reagent：,CrO3 + pyridine,特殊情况：,实验室常用方法：,Jones reagent：,CrO3 + diluted H2SO4,橙色透明,蓝绿色 不透明,鉴别！,pyridinium chlorochromate: 氯铬酸吡啶盐（PCC）,When air is pumped in, water vapor is generated.,工业上常用方法：脱氢,还原性气氛，易将产物又还
16、原为醇,10.4.1 Reactions similar to monobasic alcohol10.4.2 Reactions different from monobasic alcohol,10.4 Polybasic alcohol 多元醇,10.4.1 Reactions similar to monobasic alcohol与一元醇类似的性质,Acid-base reaction Esterifying Nucleophilic substitution Dehydration and elimination Hydrogenation (Oxidation) Dehydrog
17、enation,10.4.2 Reactions different from monobasic alcohol 多元醇的特殊性质,(A). Reaction with Cu(OH)2,Identification of 1,2-diol, or some substance with similar substructure. 用于鉴别1,2-二醇或具有邻二羟基的多元醇,Soluble, blue 蓝色 可溶,(B). Reaction with periodic acid 与高碘酸的反应,Reaction,This reaction is usually used to identify
18、 structures.,Mechanism,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,均难发生反应,Application,反应定量进行，由消耗的高碘酸的量可测定邻二醇的量 推断结构：,(C). Pinacol rearrangement 嚬哪醇重排,Pinacol 嚬哪醇,Pinacolone 嚬哪酮,邻二醇在酸作用下的重排,较不稳定的碳正离子（碳外层6个电子）,较稳定的 盐（碳外层8个电子）,甲基迁移,Which carbocation is favored ? 生成哪个碳正离子？,主产物,次产物,Which group shifts ? 哪个基团迁
19、移？,迁移能力：R-ph ph NO2-ph R CH3 H 即：提供电子、稳定正电荷能力较强的基团优先迁移,Shifting group and leaving group 迁移的立体化学要求,迁移基团与离去基团处于反式位置时较易迁移,(D). Polymerization and cyclization 聚合与成环,聚乙二醇,10.5 Preparation of alcohol(learn on your own) 10.6 Sources and usages(learn on your own),Part IIPhenols 第一部分 酚,10.7 Structure and nom
20、enclature 结构和命名,Phenol 酚,Alcohol 醇,Electron-donating conjugation, = 1.6 D,强给电子基团,Nomenclature 命名,采用芳烃命名原则。,10.8 Physical and spectroscopic properties,10.8.1 Physical properties,苯酚在冷水中微溶，加热时可无限溶解 分子间氢键 纯的酚无色，但易被空气中的氧气氧化而呈略红或褐色 毒性,10.8.1 spectroscopic data,IR,(O-H),(C-O),3610cm-1,1200cm-1,NMR,4 - 12 p
21、pm,Mass spectrometry,10.9.1 Electrophilic reactions10.9.2 Other properties,10.9 Chemical reactions,10.9.1 Electrophilic reactions,邻对位活化基,反应条件温和 反应速度快 产物邻、对位为主 容易发生多取代,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,10.9.2 Other properties 苯酚的特殊反应,(A). Acidity 酸性,若芳香基团上有吸电子基团，则酚酸性增强。,亲核试剂,可用于制备醚,可用于制备苯甲醚,(B)
22、. Reaction with FeCl3 与FeCl3的反应,适用：苯酚，萘酚及其衍生物 用途：鉴别苯酚（鉴别具有烯醇结构的化合物） 颜色：蓝色，紫色为主,紫色,烯醇结构,(C). Oxidation,对苯醌,对位取代基可能脱去,注意：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2、磺化、硝化等反应时应注意反应条件，以免被氧化,10.10 Preparations,10.10.1 Preparations of phenol苯酚的制备10.10.2 Preparations of naphthol萘酚的制备,10.10.1 Preparations of pheno
23、l 苯酚的制备,(A). Alkali Fusion of Sodium Benzene-sulfonate 苯磺酸碱融法,融熔,(B). Hydrolysis of Benzyl Chloride 氯苯水解,氯苯的制备：,(C). Cumene Oxidation 异丙苯氧化,两种化工原料,两种石化产品,10.10.2 Preparations of naphthol 萘酚的制备,(A). Alkali Fusion 碱融法,(B). Hydrolysis of -naphthalidine -萘胺水解,10.11 Sources and usages (Learn on your own),Thank you!,
