清华大学有机化学李艳梅老师课件第十章

1、Alcohols and phenols第十章第十章 醇与酚醇与酚Organic Chemistry A (1)By Prof. Li Yan-MeiTsinghua UniversityOHOHOHHOOHHOOH醇（Alcohol）酚（Phenol） Part I Alcohols 10.1 Structure, isomerization, classification and nomenclature 10.2 Physical and spectroscopic properties 10.3 Monobasic/Monohydroxyl alcohol 10.4 Polybasic

2、 alcohol 10.5 Preparation of alcohol 10.6 Sources and usagesPart 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 10.1.1 Structure 10.1.2 Isomerization 10.1.3 Classification 10.1.4

3、Nomenclature 10.1 Structure, isomerization, classification and nomenclature108.5osp3 hybridization 2DVery close to waterMany alcohols completely miscible with water 10.1.1 Structure 结构结构OH10.1.2 Isomerization 异构异构Position isomerizationOHOHOHOHOFuctional group isomerizationCarbon chain isomerization位

4、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10.1.3 Classification 分类分类 C12OHOHHOOHHOOHOHOHOHp 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10.1.4 Nomenclature 命名命名OH Deciding the longest chain to which the hydroxyl group is attached1 Decide the serial number for all carbon atoms.2 Write

5、 down the name. 3OH123452-pentanolOH5,5-dimethyl-2-hexanolCH3OH5-methyl-3-hexanolCH3OH5-methylhex-4-en-2-olOH(E)-pent-3-en-1-olOHO2N4-nitrophenolInter molecular hydrogen bondBoiling pointMelting pointSimple alcohols completely miscible with water与水形成氢键与水形成氢键低级醇一般与水任意混溶低级醇一般与水任意混溶OHHOHOOHHOHOHH10.2 P

6、hysical and spectroscopic properties10.2.1 Physical properties分子间氢键导致熔点、沸点较高分子间氢键导致熔点、沸点较高Simple alcohols may form co-crystals with inorganic salts.低级醇与一些无机盐（如：低级醇与一些无机盐（如：MgCl2、CaCl2、CuSO4等）形成结晶状等）形成结晶状的分子化合物的分子化合物 结晶醇结晶醇（醇化物醇化物）MgCl2, CuSO4 MgCl2 6 CH3OHCaCl2 4 C2H5OHCaCl2 4 CH3OH用途：除去有机溶剂中少量的醇用途：

7、除去有机溶剂中少量的醇 将醇与其它有机物分开将醇与其它有机物分开危害：不可用危害：不可用MgCl2、CaCl2、CuSO4等来干燥低级醇等来干燥低级醇10.2.1 Spectrometry(O-H)(C-O)3640cm-13630cm-1OHOHOH3620cm-11050cm-11100cm-11150cm-1IR(O-H)35503450cm-1(O-H)34003200cm-1in inter molecular hydrogen bonding systemsOHHOOHHOHO(-OH)36003500cm-1in intra molecular hydrogen bonding

8、systems(-OH)32003500cm-1multi molecule cluster(-OH)34003200cm-1OHOHNOOHO(O-H)3710cm-1(O-H)3300cm-1(O-H)36003450cm-1IR of OH bond in water moleculeSolid, iceCrystallized waterLiquid waterCH2OHNMR0.5 - 5.5 3.7CHCHOH15 - 19活泼氢活泼氢 10.3.1 Acidity and basicity 10.3.2 Esterifying 10.3.3 Nucleophilic substi

9、tution 10.3.4 Dehydration and elimination10.3 Monobasic/Monohydroxyl alcoholBrief introductionCHCHHHOHOH is not a good leaving group.Proton is often required to change the bad leaving group OH into a good leaving group OH2+OH2Nu:OHHNuH2OOHNu:好的离去基团好的离去基团10.3.1 Acidity and basicity 酸、碱性酸、碱性Stronger a

10、cidityWeakeracidity(1) Relative acidity 酸性顺序酸性顺序ROHRO+HOHOHOH(A) Acidity 酸性酸性原因：溶剂化效应的影响原因：溶剂化效应的影响More solvation leads to more stable positive ion. OHOHOH溶剂化效应的影响：溶剂化效应的影响：Stronger acidityWeakeracidityInductive effectInductive effectElectron cloud pulled OHClOHOHClOHFFF诱导效应的影响：诱导效应的影响：Na(2) Reactio

11、n with metals 与金属的反应与金属的反应KCaMgAlRbSrBaCs2 ROHNa2 RONa+H2Reaction rateRCH2OH 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。(B) Basicity 碱性碱性OHOHH+OH2OHBF3OHBF3Boron trifluoride好的离

12、去基团好的离去基团 10.3.2 Esterification 酯化反应酯化反应ROH+HONO2RONO2+H2OROH+HONORONO+H2OROH+HOSO2OHROSO2OH+H2OOrganic acidInorganic acidROH +ROHOROROH +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Acyl chlorideROH+ClSO2OHROSO2OH+HClROH+RCOClRCOOR+HClAnhydrideROH +ROOROROROHORO+Mechanism 机理机理ROH +ROHOROOHOHRROHOHORH+ROH2OO

13、RHROROROH+H+SOOHOOHHORSOOHOHOORSOOHOHHOORSOOHOH2OHSOOHOORROH+ROClRCClOORROOR 10.3.3 Nucleophilic substitution 亲核取代反应亲核取代反应COHHHNu:CNuHHNucleophilic reagent 亲核试剂亲核试剂HX, PX3, SOCl2 .常见产物：常见产物：RX（RCl）ROH+HXRX+H2O(A). Reactions with HX 与与HX的反应的反应3oROH2oROH1oROHReactivityHIHBrHClHFMechanism：H+及及ZnCl2的作用的

14、作用 - 形形成好的离去基团成好的离去基团ROHH+ROH2ROHZnCl2ROHZnCl2SN1 or SN2 ?Generally, 1o ROH follows SN2 mechanism, while 2o and 3o ROH follows SN1 mechanism, which is often coupled with an anion rearrangement.OHH+OH2hydride shiftHBrBrOH易发生重排Mechanism-neighboring group participation 邻基邻基参与参与BrBrHHOH+BrBrHH2OBrBrHBro

15、monium ionClBrBrHClLucas reagent: Lucas试剂试剂ROH+HClZnCl2RCl+H2OReactivity 反应性反应性3oROH2oROH1oROHReaction 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(B). Reactions with

16、 PXnReaction3ROH+PBr33RBr3+H3PO3MechanismRCl is often prepared with PCl5 and the corresponding alcohol, while RI with P, iodine, and the corresponding alcohol.ROH + PBr3ROPBr2 + HBrRH2COPBr2Br +RCH2Br + OPBr2不重排不重排(C) Reactions with SOCl2ROH+SOCl2RCl+SO2+HClNo rearrangement!SOCl2HClClOHClOH不重排不重排10.

17、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 ROHHOR+H2SO4RORetherExampleA side reaction of alcohol dehydration to form ethene.You have performed this experiment at high school.C2H5OHHOC2H5+H2SO4C2H5OC2H51400CMechanismOH2CH3CH2OHH2SO4CH3CH2OH2+HSO4CH3CH2CH3CH2OH+C2H5OC2H5HH

18、SO4C2H5OC2H5+H2SO4本质：亲核取代反应本质：亲核取代反应(B) Intramolecular dehydration CCOHHH+170180oCCC+H2OExample+H2OH3CCH2OHH2SO4180oCH2CCH2This reaction follows an E1 elimination mechanism.Mechanism3oROH2oROH1oROHReactivity+HH3CCH2OHH2SO4H2CCH2H3CCH2OH2+H2SO4H3CCH2OH2SlowFastH3CCH2+H2OH2CCH2HFastProductu Follows Za

19、itzevs ruleu E form本质：消去反应本质：消去反应u Rearrangement occurs when a more stable anion is formed.OHH3PO4+3%64%注意：注意：u Competition between intermolecular and intramolecular reaction often exists. Under high temperature, elimination is favored, otherwise intramolecular dehydration.10.3.5 Oxidation 氧化反应氧化反应R

20、CH2OHORRCHOHORRRCOHOROHORRON.R.O: Na2Cr2O7, HNO3, KMnO4一般地：2 KMnO4+3 MnSO4+4 NaOH5 MnO2+K2SO4+2 Na2SO4+2 H2OOH25oCCHOSarrett reagent：CrO3 + pyridine特殊情况：RCH2OHSarrett reagentRCHOSarrett reagentRROHRRO实验室常用方法：实验室常用方法：Jones reagent：CrO3 + diluted H2SO4RCH2OHJones reagentRCHOJones reagentRROHRRO+Cr3+Cr

21、3+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） NCrO3, HClNHClCrO3PCCROHRROHCu325oCRORCu325oCROH+H2+H2When air is pumped in, water vapor is generated.OHCu325oCOH+H2O+O2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 10.4.1 Reactions similar to monobasic alcohol 10.4.2 Rea

22、ctions different from monobasic alcohol10.4 Polybasic alcohol 多元醇多元醇10.4.1 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)Dehydrogenation10.4.2 Reactions different from monobasic alcoh

23、ol 多元醇的特殊性质多元醇的特殊性质(A). Reaction with Cu(OH)2RROHOHCu(OH)2(fresh)RROOCu+2 H2OuIdentification 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(B). Reaction with periodic acid 与高碘与高碘酸的反应酸的反应RROHOHRCHORORRH5IO6+HIO3+H2OReactionTh

24、is reaction is usually used to identify structures.MechanismCCOHOHIOHHOOHOHHOO+IOHOOHOHOOCCCCOOIOHOHOHO+IOHOO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：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OHOHButOHOH均难发生反应均难发生反应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：H3CHCHCHCCH2CH3OHOHOH2 H

25、5IO6H3CCHOHOHHCOHHOOHHCCH2CH3OHHOH3CCHOCHOOHCHCH2CH3O(C). Pinacol rearrangement 嚬哪醇重排嚬哪醇重排OHHOH2SO4(HCl)OOHHOH+OHH2OOHOHH+OPinacol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phOHphHOH+phphHOH+phOHphmore stableOphphOphphWhich

26、 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 group shifts ? 哪个基团迁移？哪个基团迁移？OHphphHOH+OHphphOphphOphphmain product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OHHOOfastOHOHOslowShifting 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

27、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(D). Polymerization and cyclization 聚合聚合与成环与成环OHOHOH+HOOHH+2OOHOOHH+nCH2CH2On聚乙二醇聚乙二醇10.5 Preparation of alcohol (learn on your own)10.6 Sources and usages (learn on your own)10.7 Structure and nomenclature 结构和命名结构和命名OHOHPhenol酚酚Alcohol醇醇OHOHOHOHElectron-donating co

28、njugation = 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。10.8 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10.8.1 spectroscopic data IR(O-H)(C-O)OH3610cm-11200cm-1NMROH4 - 12

29、ppmMass spectrometryOHOHHHHm/z = 66m/z = 65H- CHOOHm/z = 108OHm/z = 107- COHHm/z = 79- H2m/z = 77 10.9.1 Electrophilic reactions 10.9.2 Other properties10.9 Chemical reactions 10.9.1 Electrophilic reactionsOH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OHBr2OHBrBrBrOHBr2OHBr0oC, C

30、S2OHBr+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 苯酚的特殊反应苯酚的特殊反应(A). Acidity 酸性酸性OH1015.74H2OC2H5OH15.9H2CO3C2H225NH334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。OHNaOHONaCO2OHSOOOOCH3H3COCH3RXOR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6 C6H5OH+FeCl3H3Fe(OC6H5)+3 HCl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