清華大學(xué)有機(jī)化學(xué)李艷梅老師課件第10章

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(jié)構(gòu)結(jié)構(gòu)OH10.1.2 Isomerization 異構(gòu)異構(gòu)Position isomerizationOHOHOHOHOFuctional group isomerizationCarbon chain isomerization位

4、置異構(gòu)位置異構(gòu)碳架異構(gòu)碳架異構(gòu)官能團(tuán)異構(gòu)官能團(tuán)異構(gòu)10.1.3 Classification 分類(lèi)分類(lèi) C12OHOHHOOHHOOHOHOHOHp 根據(jù)羥基數(shù)目：一元醇 二元醇 三元醇p 根據(jù)所連的碳原子不同：一級(jí)醇（伯醇） 二級(jí)醇（仲醇） 三級(jí)醇（叔醇）p 根據(jù)所含碳原子數(shù)目：低級(jí)醇 中級(jí)醇 高級(jí)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(jí)醇一般與水任意混溶低級(jí)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(dǎo)致熔點(diǎn)、沸點(diǎn)較高分子間氫鍵導(dǎo)致熔點(diǎn)、沸點(diǎn)較高Simple alcohols may form co-crystals with inorganic salts.低級(jí)醇與一些無(wú)機(jī)鹽（如：低級(jí)醇與一些無(wú)機(jī)鹽（如：MgCl2、CaCl2、CuSO4等）形成結(jié)晶狀等）形成結(jié)晶狀的分子化合物的分子化合物 結(jié)晶醇結(jié)晶醇（醇化物醇化物）MgCl2, CuSO4 MgCl2 6 CH3OHCaCl2 4 C2H5OHCaCl2 4 CH3OH用途：除去有機(jī)溶劑中少量的醇用途：

7、除去有機(jī)溶劑中少量的醇 將醇與其它有機(jī)物分開(kāi)將醇與其它有機(jī)物分開(kāi)危害：不可用危害：不可用MgCl2、CaCl2、CuSO4等來(lái)干燥低級(jí)醇等來(lái)干燥低級(jí)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 alcoholLone pair electrons Basicity NucleophileAcidity Ionization Reacting with alkali metalsLabile beta-hydrogen Elimination Oxidation DehydrationBrief introductionCHCHHHOHOH is not a good leaving group.Proton is often required to

10、 change the bad leaving group OH into a good leaving group OH2+OH2Nu:OHHNuH2OOHNu:好的離去基團(tuán)好的離去基團(tuán)10.3.1 Acidity and basicity 酸、堿性酸、堿性Stronger acidityWeakeracidity(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(yīng)的影響原因：溶劑化效應(yīng)的影響More solvation leads to more stable positive ion. OHOHOH溶劑化效應(yīng)

11、的影響：溶劑化效應(yīng)的影響：Stronger acidityWeakeracidityInductive effectInductive effectElectron cloud pulled OHClOHOHClOHFFF誘導(dǎo)效應(yīng)的影響：誘導(dǎo)效應(yīng)的影響：Na(2) Reaction with metals 與金屬的反應(yīng)與金屬的反應(yīng)KCaMgAlRbSrBaCs2 ROHNa2 RONa+H2Reaction rateRCH2OH R2CHOH R3COHApplicationsDeal with such metals with alcohol, reducing reaction rate,

12、 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O(shè)HOHH+OH2OHBF3OHBF3Boron trifluoride好的離去基團(tuán)好的離去基團(tuán) 10.3.2 Esterification 酯化反應(yīng)酯化反應(yīng)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

13、硝酸某酯硫酸氫某酯硫酸氫某酯Acyl chlorideROH+ClSO2OHROSO2OH+HClROH+RCOClRCOOR+HClAnhydrideROH +ROOROROROHORO+Mechanism 機(jī)理機(jī)理ROH +ROHOROOHOHRROHOHORH+ROH2OORHROROROH+H+SOOHOOHHORSOOHOHOORSOOHOHHOORSOOHOH2OHSOOHOORROH+ROClRCClOORROOR 10.3.3 Nucleophilic substitution 親核取代反應(yīng)親核取代反應(yīng)COHHHNu:CNuHHNucleophilic reagent 親核試劑

14、親核試劑HX, PX3, SOCl2 .常見(jiàn)產(chǎn)物：常見(jiàn)產(chǎn)物：RX（RCl）ROH+HXRX+H2O(A). Reactions with HX 與與HX的反應(yīng)的反應(yīng)3oROH2oROH1oROHReactivityHIHBrHClHFMechanism：H+及及ZnCl2的作用的作用 - 形成好的離去基團(tuán)形成好的離去基團(tuán)ROHH+ROH2ROHZnCl2ROHZnCl2SN1 or SN2 ?Generally, 1o ROH follows SN2 mechanism, while 2o and 3o ROH follows SN1 mechanism, which is often cou

15、pled with an anion rearrangement.OHH+OH2hydride shiftHBrBrOH易發(fā)生重排Mechanism-neighboring group participation 鄰基參與鄰基參與BrBrHHOH+BrBrHH2OBrBrHBromonium ionClBrBrHClLucas reagent: Lucas試劑試劑ROH+HClZnCl2RCl+H2OReactivity 反應(yīng)性反應(yīng)性3oROH2oROH1oROHReaction occurs immediately立刻反應(yīng)立刻反應(yīng)Reaction occurs after 25 min 片刻

16、片刻(2-5分鐘分鐘)后反應(yīng)后反應(yīng)Reaction occurs when heated 加熱才反應(yīng)加熱才反應(yīng)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 PXnReaction3ROH+PBr33RBr3+H3PO3MechanismRCl is often prepared with PCl5 and the corresponding alcohol, while RI with P, iodine, and the corresponding alcohol.R

17、OH + 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10.3.4 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 hav

18、e performed this experiment at high school.C2H5OHHOC2H5+H2SO4C2H5OC2H51400CMechanismOH2CH3CH2OHH2SO4CH3CH2OH2+HSO4CH3CH2CH3CH2OH+C2H5OC2H5HHSO4C2H5OC2H5+H2SO4本質(zhì)：親核取代反應(yīng)本質(zhì)：親核取代反應(yīng)(B) Intramolecular dehydration CCOHHH+170180oCCC+H2OExample+H2OH3CCH2OHH2SO4180oCH2CCH2This reaction follows an E1 eliminati

19、on mechanism.Mechanism3oROH2oROH1oROHReactivity+HH3CCH2OHH2SO4H2CCH2H3CCH2OH2+H2SO4H3CCH2OH2SlowFastH3CCH2+H2OH2CCH2HFastProductu Follows Zaitzevs ruleu E form本質(zhì)：消去反應(yīng)本質(zhì)：消去反應(yīng)u Rearrangement occurs when a more stable anion is formed.OHH3PO4+3%64%注意：注意：u Competition between intermolecular and intramole

20、cular reaction often exists. Under high temperature, elimination is favored, otherwise intramolecular dehydration.10.3.5 Oxidation 氧化反應(yīng)氧化反應(yīng)RCH2OHORRCHOHORRRCOHOROHORRON.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：RCH2OHS

21、arrett reagentRCHOSarrett reagentRROHRRO實(shí)驗(yàn)室常用方法：實(shí)驗(yàn)室常用方法：Jones reagent：CrO3 + diluted H2SO4RCH2OHJones reagentRCHOJones reagentRROHRRO+Cr3+Cr3+橙色透明橙色透明藍(lán)綠色藍(lán)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 vapo

22、r is generated.OHCu325oCOH+H2O+O2工業(yè)上常用方法：脫氫工業(yè)上常用方法：脫氫還原性氣氛，還原性氣氛，易將產(chǎn)物又還易將產(chǎn)物又還原為醇原為醇 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 to monobasic alcohol 與一元醇類(lèi)似的性質(zhì)與一元醇類(lèi)似的性質(zhì)Acid-base reactionEsterifyin

23、gNucleophilic substitutionDehydration and eliminationHydrogenation (Oxidation)Dehydrogenation10.4.2 Reactions different from monobasic alcohol 多元醇的特殊性質(zhì)多元醇的特殊性質(zhì)(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

24、,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(lán)色藍(lán)色 可溶可溶(B). Reaction with periodic acid 與高碘酸的反應(yīng)與高碘酸的反應(yīng)RROHOHRCHORORRH5IO6+HIO3+H2OReactionThis reaction is usually used to identify structures.MechanismCCOHOHIOHHOOHOHHOO+IOHOOHOHOOCCCCOOIOHOHOHO+IOHOO環(huán)狀酯中間體環(huán)狀酯中間體氧化值：氧化值：7氧化值：氧化值：5注意：環(huán)狀酯中間體，要求兩個(gè)羥基處于順式注

25、意：環(huán)狀酯中間體，要求兩個(gè)羥基處于順式OHOHButOHOH均難發(fā)生反應(yīng)均難發(fā)生反應(yīng)Application p 反應(yīng)定量進(jìn)行，由消耗的高碘酸的量可測(cè)定鄰二醇的量反應(yīng)定量進(jìn)行，由消耗的高碘酸的量可測(cè)定鄰二醇的量p 推斷結(jié)構(gòu)：推斷結(jié)構(gòu)：H3CHCHCHCCH2CH3OHOHOH2 H5IO6H3CCHOHOHHCOHHOOHHCCH2CH3OHHOH3CCHOCHOOHCHCH2CH3O(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

26、鄰二醇在酸作用下的重排的重排較不穩(wěn)定的碳較不穩(wěn)定的碳正離子（碳外正離子（碳外層層6個(gè)電子）個(gè)電子）較穩(wěn)定的較穩(wěn)定的 鹽（碳外層鹽（碳外層8個(gè)電子）個(gè)電子）钅钅 羊羊甲基遷移甲基遷移phOHphHOH+phphHOH+phOHphmore stableOphphOphphWhich carbocation is favored ? 生成哪個(gè)碳正離子？生成哪個(gè)碳正離子？主產(chǎn)物主產(chǎn)物次產(chǎn)物次產(chǎn)物Which group shifts ? 哪個(gè)基團(tuán)遷移？哪個(gè)基團(tuán)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

27、 ph NO2-ph R CH3 H即：提供電子、穩(wěn)定正電荷能即：提供電子、穩(wěn)定正電荷能 力較強(qiáng)的基團(tuán)優(yōu)先遷移力較強(qiáng)的基團(tuán)優(yōu)先遷移OHHOOfastOHOHOslowShifting group and leaving group 遷移的立體化學(xué)要求遷移的立體化學(xué)要求遷移基團(tuán)與離去基團(tuán)遷移基團(tuán)與離去基團(tuán)處于反式位置時(shí)較易處于反式位置時(shí)較易遷移遷移(D). Polymerization and cyclization 聚合與成環(huán)聚合與成環(huán)OHOHOH+HOOHH+2OOHOOHH+nCH2CH2On聚乙二醇聚乙二醇10.5 Preparation of alcohol (learn on you

28、r own)10.6 Sources and usages (learn on your own)10.7 Structure and nomenclature 結(jié)構(gòu)和命名結(jié)構(gòu)和命名OHOHPhenol酚酚Alcohol醇醇OHOHOHOHElectron-donating conjugation = 1.6 D強(qiáng)給電子基團(tuán)強(qiáng)給電子基團(tuán)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(shí)可無(wú)限溶解苯酚在冷水中微溶，加

29、熱時(shí)可無(wú)限溶解p分子間氫鍵分子間氫鍵p純的酚無(wú)色，但易被空氣中的氧氣氧化而呈純的酚無(wú)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 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 Che

30、mical reactions 10.9.1 Electrophilic reactionsOH鄰對(duì)位活化基鄰對(duì)位活化基反應(yīng)條件溫和反應(yīng)條件溫和反應(yīng)速度快反應(yīng)速度快產(chǎn)物鄰、對(duì)位為主產(chǎn)物鄰、對(duì)位為主容易發(fā)生多取代容易發(fā)生多取代OHBr2OHBrBrBrOHBr2OHBr0oC, CS2OHBr+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(chǎn)物10.9.2 Other properties 苯酚的特殊反應(yīng)苯酚的特殊反應(yīng)(A). Acidity 酸性酸性O(shè)H1015.74H2OC2H5OH15.9H2CO3C2H225NH334若芳香基團(tuán)上有吸電子基團(tuán)，則酚酸性增強(qiáng)。若芳香基團(tuán)上有吸電子基團(tuán)，則酚酸性增強(qiáng)。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(yīng)的反應(yīng)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(jié)構(gòu)的化合物）（