1、Alcohols and phenols第十章第十章 醇與酚醇與酚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 結構結構OH10.1.2 Isomerization 異構異構Position isomerizationOHOHOHOHOFuctional group isomerizationCarbon chain isomerization位

4、置異構位置異構碳架異構碳架異構官能團異構官能團異構10.1.3 Classification 分類分類 C12OHOHHOOHHOOHOHOHOHp 根據羥基數目：一元醇 二元醇 三元醇p 根據所連的碳原子不同：一級醇（伯醇） 二級醇（仲醇） 三級醇（叔醇）p 根據所含碳原子數目：低級醇 中級醇 高級醇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與水形成氫鍵與水形成氫鍵低級醇一般與水任意混溶低級醇一般與水任意混溶OHHOHOOHHOHOHH10.2 P

6、hysical and spectroscopic properties10.2.1 Physical properties分子間氫鍵導致熔點、沸點較高分子間氫鍵導致熔點、沸點較高Simple alcohols may form co-crystals with inorganic salts.低級醇與一些無機鹽（如：低級醇與一些無機鹽（如：MgCl2、CaCl2、CuSO4等）形成結晶狀等）形成結晶狀的分子化合物的分子化合物 結晶醇結晶醇（醇化物醇化物）MgCl2, CuSO4 MgCl2 6 CH3OHCaCl2 4 C2H5OHCaCl2 4 CH3OH用途：除去有機溶劑中少量的醇用途：

7、除去有機溶劑中少量的醇 將醇與其它有機物分開將醇與其它有機物分開危害：不可用危害：不可用MgCl2、CaCl2、CuSO4等來干燥低級醇等來干燥低級醇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活潑氫活潑氫 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:好的離去基團好的離去基團10.3.1 Acidity and basicity 酸、堿性酸、堿性Stronger a

10、cidityWeakeracidity(1) Relative acidity 酸性順序酸性順序ROHRO+HOHOHOH(A) Acidity 酸性酸性原因：溶劑化效應的影響原因：溶劑化效應的影響More solvation leads to more stable positive ion. OHOHOH溶劑化效應的影響：溶劑化效應的影響：Stronger acidityWeakeracidityInductive effectInductive effectElectron cloud pulled OHClOHOHClOHFFF誘導效應的影響：誘導效應的影響：Na(2) Reactio

11、n with metals 與金屬的反應與金屬的反應KCaMgAlRbSrBaCs2 ROHNa2 RONa+H2Reaction rateRCH2OH R2CHOH R3COHApplicationsDeal with such metals with alcohol, reducing reaction rate, avoiding explosion.Alcoholic metals are good nucleophiles.醇金屬可作為好的親核試劑醇金屬可作為好的親核試劑。(B) Basicity 堿性堿性OHOHH+OH2OHBF3OHBF3Boron trifluoride好的離

12、去基團好的離去基團 10.3.2 Esterification 酯化反應酯化反應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亞硝酸某酯亞硝酸某酯硫酸氫某酯硫酸氫某酯Acyl chlorideROH+ClSO2OHROSO2OH+HClROH+RCOClRCOOR+HClAnhydrideROH +ROOROROROHORO+Mechanism 機理機理ROH +ROHOROOHOHRROHOHORH+ROH2OO

13、RHROROROH+H+SOOHOOHHORSOOHOHOORSOOHOHHOORSOOHOH2OHSOOHOORROH+ROClRCClOORROOR 10.3.3 Nucleophilic substitution 親核取代反應親核取代反應COHHHNu:CNuHHNucleophilic reagent 親核試劑親核試劑HX, PX3, SOCl2 .常見產物：常見產物：RX（RCl）ROH+HXRX+H2O(A). Reactions with HX 與與HX的反應的反應3oROH2oROH1oROHReactivityHIHBrHClHFMechanism：H+及及ZnCl2的作用的

14、作用 - 形形成好的離去基團成好的離去基團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易發生重排Mechanism-neighboring group participation 鄰基鄰基參與參與BrBrHHOH+BrBrHH2OBrBrHBro

15、monium ionClBrBrHClLucas reagent: Lucas試劑試劑ROH+HClZnCl2RCl+H2OReactivity 反應性反應性3oROH2oROH1oROHReaction occurs immediately立刻反應立刻反應Reaction occurs after 25 min 片刻片刻(2-5分鐘分鐘)后反應后反應Reaction occurs when heated 加熱才反應加熱才反應C6以下一元醇以下一元醇 溶于溶于HCl 不溶于不溶于HCl 變渾變渾 由于鑒別由于鑒別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 脫水與消除脫水與消除(A) Intermolecular 分子間脫水分子間脫水 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本質：親核取代反應本質：親核取代反應(B) Intramolecular dehydration CCOHHH+170180oCCC+H2OExample+H2OH3CCH2OHH2SO4180oCH2CCH2This reaction follows an E1 elimination mechanism.Mechanism3oROH2oROH1oROHReactivity+HH3CCH2OHH2SO4H2CCH2H3CCH2OH2+H2SO4H3CCH2OH2SlowFastH3CCH2+H2OH2CCH2HFastProductu Follows Za

19、itzevs ruleu E form本質：消去反應本質：消去反應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 氧化反應氧化反應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特殊情況：RCH2OHSarrett reagentRCHOSarrett reagentRROHRRO實驗室常用方法：實驗室常用方法：Jones reagent：CrO3 + diluted H2SO4RCH2OHJones reagentRCHOJones reagentRROHRRO+Cr3+Cr

21、3+橙色透明橙色透明藍綠色藍綠色不透明不透明鑒別！鑒別！pyridinium chlorochromate: 氯鉻酸吡啶鹽氯鉻酸吡啶鹽（PCC） NCrO3, HClNHClCrO3PCCROHRROHCu325oCRORCu325oCROH+H2+H2When air is pumped in, water vapor is generated.OHCu325oCOH+H2O+O2工業上常用方法：脫氫工業上常用方法：脫氫還原性氣氛，還原性氣氛，易將產物又還易將產物又還原為醇原為醇 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 與一元醇類似的性質與一元醇類似的性質Acid-base reactionEsterifyingNucleophilic substitutionDehydration and eliminationHydrogenation (Oxidation)Dehydrogenation10.4.2 Reactions different from monobasic alcoh

23、ol 多元醇的特殊性質多元醇的特殊性質(A). Reaction with Cu(OH)2RROHOHCu(OH)2(fresh)RROOCu+2 H2OuIdentification of 1,2-diol, or some substance with similar substructure. 用于鑒別用于鑒別1,2-1,2-二醇或具有鄰二羥基的多元醇二醇或具有鄰二羥基的多元醇Soluble, blue藍色藍色 可溶可溶(B). Reaction with periodic acid 與高碘與高碘酸的反應酸的反應RROHOHRCHORORRH5IO6+HIO3+H2OReactionTh

24、is reaction is usually used to identify structures.MechanismCCOHOHIOHHOOHOHHOO+IOHOOHOHOOCCCCOOIOHOHOHO+IOHOO環狀酯中間體環狀酯中間體氧化值：氧化值：7氧化值：氧化值：5注意：環狀酯中間體，要求兩個羥基處于順式注意：環狀酯中間體，要求兩個羥基處于順式OHOHButOHOH均難發生反應均難發生反應Application p 反應定量進行，由消耗的高碘酸的量可測定鄰二醇的量反應定量進行，由消耗的高碘酸的量可測定鄰二醇的量p 推斷結構：推斷結構：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嚬哪酮嚬哪酮鄰二醇在酸作用下鄰二醇在酸作用下的重排的重排較不穩定的碳較不穩定的碳正離子（碳外正離子（碳外層層6個電子）個電子）較穩定的較穩定的 鹽（碳外層鹽（碳外層8個電子）個電子）钅钅 羊羊甲基遷移甲基遷移phOHphHOH+phphHOH+phOHphmore stableOphphOphphWhich

26、 carbocation is favored ? 生成哪個碳正離子？生成哪個碳正離子？主產物主產物次產物次產物Which group shifts ? 哪個基團遷移？哪個基團遷移？OHphphHOH+OHphphOphphOphphmain product甲基遷移甲基遷移苯基遷移苯基遷移遷移能力：遷移能力： R-ph ph NO2-ph R CH3 H即：提供電子、穩定正電荷能即：提供電子、穩定正電荷能 力較強的基團優先遷移力較強的基團優先遷移OHHOOfastOHOHOslowShifting group and leaving group 遷移的立體化學要求遷移的立體化學要求遷移基團與離

27、去基團遷移基團與離去基團處于反式位置時較易處于反式位置時較易遷移遷移(D). Polymerization and cyclization 聚合聚合與成環與成環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 結構和命名結構和命名OHOHPhenol酚酚Alcohol醇醇OHOHOHOHElectron-donating co

28、njugation = 1.6 D強給電子基團強給電子基團Nomenclature 命名命名采用芳烴命名原則。采用芳烴命名原則。10.8 Physical and spectroscopic properties10.8.1 Physical propertiesp苯酚在冷水中微溶，加熱時可無限溶解苯酚在冷水中微溶，加熱時可無限溶解p分子間氫鍵分子間氫鍵p純的酚無色，但易被空氣中的氧氣氧化而呈純的酚無色，但易被空氣中的氧氣氧化而呈略紅或褐色略紅或褐色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鄰對位活化基鄰對位活化基反應條件溫和反應條件溫和反應速度快反應速度快產物鄰、對位為產物鄰、對位為主主容易發生多取代容易發生多取代OHBr2OHBrBrBrOHBr2OHBr0oC, C

30、S2OHBr+白色極靈敏（10ppm即可顯色）可用于鑒別苯酚控制條件才可獲得一鹵代產物10.9.2 Other properties 苯酚的特殊反應苯酚的特殊反應(A). Acidity 酸性酸性OH1015.74H2OC2H5OH15.9H2CO3C2H225NH334若芳香基團上有吸電子基團，則酚酸性增強。若芳香基團上有吸電子基團，則酚酸性增強。OHNaOHONaCO2OHSOOOOCH3H3COCH3RXOR親核試劑可用于制備醚可用于制備苯甲醚(B). Reaction with FeCl3 與與FeCl3的反應的反應6 C6H5OH+FeCl3H3Fe(OC6H5)+3 HCl適用：苯酚，萘酚及其衍生物適用：苯酚，萘酚及其衍生物用途：鑒別苯酚用途：鑒別苯酚 （鑒別具有烯醇結構的化合物）（鑒別具有烯醇結構的化合物）顏