有機化學(xué)上冊課件.朱衛(wèi)民10醇醚

If,asanorganicchemist,youwereallowedtochoosethetencompoundswithwhichtobestrandedonadesertisland,youwouldalmostcertainlypickalcohols.Youwoulduseyouralcoholsnotonlyasrawmaterials,butfrequentlyasthesolvents.Finally,hotandtiredafteralongdayinthelaboratory,youcouldperhapsrelaxoveranalcoholic(1R,4R)--2-環(huán)己烯-1,4-二醇HOIf,asanorganicchemist,youwereallowedtochoosethetencompoundswithwhichtobestrandedonadesertisland,youwouldalmostcertainlypickalcohols.Youwoulduseyouralcoholsnotonlyasrawmaterials,butfrequentlyasthesolvents.Finally,hotandtiredafteralongdayinthelaboratory,youcouldperhapsrelaxoveranalcoholic(1R,4R)--2-環(huán)己烯-1,4-二醇HOOHHHH HHHHHHHOOHHHHOH 2CHHHH4-羥甲基-1,8-辛二2-苯基-2-丙苯甲醇芐環(huán)戊基甲醇(1S,2S)-2-甲基環(huán)己醇 ChapterChapter10AlcoholsandAlcohols(醇)R-R-thiol(硫醇10.1Nomenclature,Classificationand10.1.15,6,6-5-乙基-2-庚(E)-6,7-二甲基-6-壬烯-1-HHO(2R,5S)-7-甲基-2,5-H3C1-1-10.1.2OH RC +primaryalcohols(伯醇,1o醇Rsecondaryalcohols(仲醇2o醇)tertiaryalcohols(叔醇,3o醇)RCR'O+R脂肪一元 脂環(huán)芳香多元RCOH+R10.1.3HHHHH H 10.2Spectroscopy(光譜學(xué)IR(紅外醇O—H伸縮振動:游離羥基 (尖峰,強度不定),締合羥基3500~3300(寬峰)(形成氫鍵后基團的伸縮頻率都會下降，譜帶變寬)醇C-O伸縮振動CHCHCHCHCHCH1-己順-1順-12-環(huán)戊二醇在低頻區(qū)有紅外吸收，既使稀釋該吸收峰也不；反-12-環(huán)戊二醇無此吸收，為什么？NMR(核磁氫譜羥基質(zhì)子δ氫鍵使羥基質(zhì)子共振信號移向低場,常是一個較寬的單峰分子內(nèi)氫鍵,其化 移變化與溶液濃度無關(guān)加入幾滴重水(DO),再測定圖譜，會使羥基HO-CH2-MS(質(zhì)譜醇的分子離子峰M經(jīng)常較弱,甚至看不到,M-18或M-15或M-29峰豐度較高┓10.310.3Acidityandbasic/COHSN2or -OHisaleavinggroup(very++E1orFormationofesters(酯andsulfonates(磺酸酯)10.3.1AcidityandBasic/ROH+HORO-+HH+O1o>2o>3o共軛堿的堿性Alkoxideion(stablizedbysolution)RSOH>RCOOH>ArOH>HO>ROH>RC?CH>H>NH>共軛堿的堿性？Cl3CCH2OH>CH3CH2OH>>>RONa+HORONa+RC≡CHNH+RC≡CNaROH+NaNHROH+>>>ROH+ROH+RC≡CNaNaNH+RONa+R'H+Reactionwithactivemetals(與活潑金屬反應(yīng)KNaMgROH+NaROH+NaH(CH)CHOH+(CH3)3COH+RONaH2醇鈉親核試RONa+(CH3)3COK大體積強親核性較弱BasicBasic/GoodleavingHCOH+HACOH+質(zhì)子化鹽ROH+ ROH ROH+ROHBF55℃(CH)COCH(CH)CBr+CH HCC叔鹵代烷的溶劑解(S1),醇的親核性 10.3.2FormationofestersandR'COOH,(R'CO)2Oor R'COOR?；磻?yīng)ROH+ RONO2硝酸 2ROH+ RONO亞硝酸 硝基化合The1998NobelPrizeinMedicinewasawardedtothescientists(R.CHONO2Furchgott,L.J.Ignarro,andF.Murad)whodiscoveredthatNOisCH2ONO2importantsignalingmolecule(chemical三硝酸甘油酯 ROHROHHOP ROP ROP ROPOR ROHPOClSulfates(硫酸酯ROH+HOSOHOO 硫酸二甲酯是個很好的甲基化試劑 CH3CH2OH+ CH3CH2OCH3OSulfonates(磺酸酯Sulfonates(磺酸酯R'SOClR'SO ROH CHSCl+HCHO O SCl+HOCHCHbaseOSOCHO COH+ClTs CO -HCl R'SO2OR磺酸酯是個很好的烷基化試劑OR'SOCHR+ RCHNu+O常用親核試劑:烷氧基負(fù)離子,鹵素負(fù)離子等OSOCH CH Nu COTsinversionNuCH+-O Duetoitssuitablepropertiesandthelowcost,DEHPiswidelyusedasasticizerinmanufacturingofarticlesofPVC.sticsmaycontainto40%ofAssadKhan,abubbleteashopownerinUK10.3.310.3.3NucleophilicSubstitution(親核取代 RNu-OHisaleavinggroup(very10.3.3.1Reactionwith ReactivityofHXHI>HBr>NaBr+HSOKI+ReactivityofROHBenzyl,allyl,3o>2o>1o用Lucas試劑鑒別各類叔醇易消除，故低溫HCCOH+HCl(concd)25 HCCCl+H CH3CH2CH2CH2OH+HBr(concd)reflux1°alcoholsandmethanol——HRCH H+RCO+HH X- RCOH XCR O+ -RO+RO+ Cl-+RO+- ClR+[Zn(OH)ClZnC HCCOCl與HBr反應(yīng)速CHOCH=CHCHOH>CHCH=CHCHOH>ClCH=CHCHOH>OH Br+H Neighboring-groupParticipation(鄰基參與HCH蘇式外消旋體H H HH+CH蘇CHH HHH H+H △△ BrHBrH 赤 赤式內(nèi)消旋10.3.3.2ReactionwithOtherPX或CHOH+RBr+C2H5OH+PCl5 RCl+HCl+POClCHOHPR1°and2°seldomRCHOH+BrPBr +PBr+Br Br-+RCH+PBrRCHBr+HOPBrHAgoodleavingCH)CHCHOH+PBr-10to0C(CH)CHCH4 (55-SOCl(亞硫酰氯氯化亞砜ROH+SOCl2 Cl+HCl+1°and2°alcoholsseldomrearrangementretentionofA3°amineisaddedtopromotethereaction——inversionofconfiguration pyridine+10.3.3.310.3.3.3ReactionsviaSulfonatesorSulfates(通過磺酸酯或硫酸酯應(yīng)OROS構(gòu)型保構(gòu)型翻OHCOSOCH堿CH+10.3.4Elimination——IntermolecularDehydrationofAlcohols(消除反應(yīng)——醇的分子內(nèi)脫水)E1 I/10.3.5Oxidation(氧化R RCRCH RCRC10.3.5.1KMnO4andRCHOH+KMnOHO新制新制O++ MnO+++OHC OCC其他羥基以及烯鍵不受影響CHOHMnOCCCO10.3.5.2Chromicacid(鉻酸烯鍵不受影響NaCrO/HSO,CrO/HOAc,CrOPy.HCl/CHCl,CrO/HSO–acetone(Jones試劑pyridiniumchlorochromate(氯鉻酸吡啶嗡鹽)——PCC(Sarrett試劑NaCrO/HRCH2OHNaCrO/HSORCHO如果醛的沸點低，可蒸出避免進一步Na2Cr2O7/H2SO4CHCHCHCHCH 332OHOOH+CrO+CrO+HCl NHCH)CCHOH+PCC (CH)CCH OOH10.3.5.3Nitricacid(硝酸++CHOH+ +CHCHCHCHCHO10.3.5.5Pfizner-Moffatt10.3.5.4Oppenauer10.410.4ReactionsofGlycols(鄰二醇的反應(yīng)10.4.1OxidativeCleavage(氧化斷裂 鄰二醇(α-二醇),α-羥基醛/酮/酸,α-氨基醛/酮/酸,1,2-二酮(α-二酮),1-氨基-2-羥基化合物均可被高碘酸分解 OH Leadacetate(醋酸鉛)OHCHCHCHCHPhCCOHH10.4.2Pinacol10.5PreparationofAlkyl CarbonylGrignard10.5.1Via10.5.1ViaHydrolysisofAlkylHalides(通過鹵代烴的水解ReactiontionofAlkenes(通過烯烴反應(yīng)HCCHCCHCCHCCCOCOCC HO OCOHOHO,△HorXX/ CCOxymercuration-demercurationofalkenes(烯烴的羥化-去化 NaBH還 ThereactionstakeceveryrapidlyatroomTheoverallreactiongivesalcoholsinveryhighyields,usuallygreaterthan90%Rearrangementsofthecarbonskeletonseldomoccur.MercurycompoundsareextremelyMechanism(機理 MarkovnikovH antiaddition(反式加成) HO CHOHHCCCH=CHNaBHHCCCCH CH(CH)CHCHTHF-HOCH(CH)CHCH CH(CH)CHCH OHHgOAc(1h) OHH10.5.3ViaReductionofCarbonylCompoundsorDerivativesofCarboxylicCompounds(通過羰基化合物或羧酸衍生物還原)ORH[HROR[HRO[O[HRC RO[HRC RCHOH+Hydrogenation(HwithRaneynickel):AlsoreducesanyC=CbondsSodiuminalcoholLithiumaluminumhydride(LiAlH):reducesacids,esters,aldehydes,andketonesSodiumborohydride(NaBH):reducesonlyaldehydesandketones10.5.4GrignardSynthesis(格氏試劑合成法1.RMgXCO2.RCOH+RMgX CRCORCOMgX+HOH+RCOHGrignardReagentsReactwithFormaldehydetoGivea1oGrignardReagentsReactwithAllOtherAldehydestoGive2oGrignardReagentsReactwithKetonestoGive3o HRMgX+C RCOMgXRC HO+RMgX+C RCOMgXRC HRMgX+C RCOMgXRC HCHMgBr C CHCHOMgBr3 HOCHCHMgBr+COEtOCHCHCOMgX3CHCHCHOH 4)EstersReactwithTwoMolarEquivalentsofaGrignardReagenttoForm3oRMgX+COCHCHMgBr+COCHCHMgBrCO RCOMgXspontaneously COOR" Initialproduct RC RC CHCHCNHCHCHC CHCHC 如用甲酸酯，則得CHCHCHCHMgBr+也可使用 CH3CH2MgBr+CH3O HOC5)ReactionsofGrignardReagentswithRMgX+HCRCHCHOMgXHCHRCHOCHMgBr+HCCH CHCHCHOMgBrH CHCHCH6 2Et2O652 652O H+C6H5MgBr+HC EtO HCCCNa+C HCCCCONaHCCCCH CHCCMgBr+CHCCCHMgBr+CHCHCCHCH2.NH2CHCHMgBr1.OCH2.NHEthers(醚)CHOCHdiethylether乙醚)FirstgeneralanestheticCausesnauseaandvomiting,andishighly CHOC(CH)Methyltert-butylether(MTBE甲基叔丁基醚AdditivetoimprovegasolineperformanceasanantiknockagentandtoreduceemissionofCOinautomotiveexhaustgasSulfide(硫醚)10.6Structure,Classificationand10.6.1DimethylCHCH-O-CHDiethylethO O 10.6.2R-O-Rsimpleether(單醚),symmetricalether(對稱醚R-O-R’complexether(混醚),unsymmetricalether(不對稱醚 Epoxide,(環(huán)氧化合物,環(huán)氧乙烷aliphaticether(脂肪醚)aromaticether(芳香醚cyclicether(環(huán)醚OCrownether(冠醚O10.6.312123O 18-冠- 10.7醚C—O—C伸縮振動1275~1020cm(強吸收H-C-Oδ醚的分子離子峰M常較m/z=57分子離子失去m/z=87分子離子失去C3H710.810.8.110.810.8.1Autoxidation(自動氧化10.8.2形成钅羊鹽和絡(luò)合物的能力:ROR’>ROAr>RO HOR+RBF-O R+The1987NobelPrizeinChemistrywasawardedtoCharlesJ.Pedersen,DonaldJ.Cram,andn-MarieLehnfortheirworkoncrownethersandrelatedcompounds(host-guestchemisty).molecular10.8.4Acid-CatalyedRX+Reactivity:HI>HBr>>Etherswith1oalkylgroupsreactbyanHCHO H + + 3 +3 BrCH+HOAlcoholisprotonated,halideattacks,andanothermoleculeofalkylbromideisHI,CHCHHBr,O+CHCHPhenolcannotreactfurther eAllylic,benzylic,and3etherscleviaCH3C∫OCH3CBr+OCHOH+HC-混醚C-O斷裂次序:Allyl,benzyl,3°烷基>2°烷基,1°烷基,CH>芳基ArOAr’在HI作用下醚鍵不斷裂O∫ O H CFCOH,OC CCHHCCH3 32 HC CC6H5COCH3+10.8.5HydrogenolysisofBen