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《药物合成反应》（第三版）闻韧主编第六章氧化反应习题及答案1第六章氧化反应习题及答案1.根据以下指定原料、试剂和反应条件，写出其合成反应的主要产物(1)CH3CO2H,20oCCrO3(2)CCH3OSeO2(3)H2CrO4OHCH3CH(CH3)2丙酮(4)HOCH2CH2CCH2CH=CHCO2CH3CH3CH3PCC(5)CO2CH3CrO3(Py)2(6)CH3CH2CHCCH2CH3OHOMnO2(7)CH3CH=CHCO2C2H5CF3CO3H(8)(CH3)2CHCH=CHCH=CHCH2OHClCOCOClDMSO(9)OHHOH2CMo(CO)6t-BuOOH(10)O1)I2/AcOAg/AcOH/H2O2)KOH/MeOH《药物合成反应》（第三版）闻韧主编第六章氧化反应习题及答案2(11)2)NaOHCOOH1)HCO2H,H2O2(12)OH3CCH3HH3CH2SO4MeOH(13)H2O2,CH3CNCH3OH,KHCO3(14)KMnO4丙酮(15)NO1)O32)Me2S1.根据以下指定原料、试剂和反应条件，写出其合成反应的主要产物（参考答案）题号答案注释1O2HOO3CH3CH(CH3)2O4OHCCO2CH35CH3CH3CO2CH3H3CCH3O《药物合成反应》（第三版）闻韧主编第六章氧化反应习题及答案36OO7CH3CHCHCO2C2H5O8CHO9HHOH2COOJ.org.Chem.,1980,45：4825.10OHHOHOH11COONaOHHOJ.Org.Chem.,1972,37:3393.12CHCH3H3CH3COCH3OH13OHH14HOOCCOOHJ.Org.Chem.,1974,39:1535.15NOOCH3本题的教材中答案可能有误？2.在下列指定原料和产物的反应式中分别填入必需的化学试剂（或反应物）和反应条件。《药物合成反应》（第三版）闻韧主编第六章氧化反应习题及答案4(1)ClCH3ClCOOH(2)PhCH=CHCH2OHPhCH=CHCH=O(3)O(4)CHCH2CO2CH3HC(CH3)2HCHCH2CO2CH3HCHCHO(5)SHHOHNCH3H3CO2CSHHONCH3H3CO2C(6)OHOCH3OOCH3(7)OHCHOHHOHCO2HHH(8)CONH2CH(CH3)2CONH2CH(CH3)2O(9)OHOHO(10)H2C=CHCH(OC2H5)2H2CCHCH(OC2H5)2OHOH《药物合成反应》（第三版）闻韧主编第六章氧化反应习题及答案5(11)CH2CHCH2CH2OCPh3CH3OCHCH2CH2OCPh3CH3(12)PhCOCH2CH2COPhPhCOCHCHCOPh2.在下列指定原料和产物的反应式中分别填入必需的化学试剂（或反应物）和反应条件。（参考答案）题号答案注释11.KMnO4,H2O;2.HCl2CrO3·(Py)2J.Org.Chem.,1969,34:1979.3CrO3·(Py)2J.Org.Chem.,1969,34:3587.4CrO3·(Py)2J.Org.Chem.,1979,44:2441.5DMSO,Ac2O6Org.Lett.,2003,5:3049.7Ag2O8J.Org.Chem.,1992,57:6696.9CH3COOOH,NaHCO3J.Org.Chem.,1987,52:4898.10KMnO4,H2O,5℃111.O3;2.Zn,H2OJ.Org.Chem.,1972,37:2877.12SeO2,80%AcOH(aq.)3.阅读（翻译）以下有关反应操作的原文，请在理解基础上写出：（1）此反应的完整反应式（原料、试剂和主要反应条件）；（2）此反应的反应机理（历程）。(1)Dipyridinechromium(VI)oxide(Note1).Adry,1-l.,three-neckedflaskfittedwithasealedmechanicalstirrer,athermometer,andadryingtube,ischargedwith500ml.ofanhydrouspyridine(Note2),whichisstirredandcooledtoapproximately15°(Note3)withanicebath.Thedryingtubeisperiodicallyremovedand68g.(0.68mole)ofanhydrouschromium(VI)oxide(Note4)isaddedinportionsthroughtheneckoftheflaskovera30-minuteperiod.Thechromiumtrioxideshouldbeaddedatsucharatethatthetemperaturedoesnotexceed20°andinsuchamannerthattheoxidemixesrapidlywiththepyridineanddoesnotadheretothesideoftheflask(Note5).Asthechromiumtrioxideisadded,anintenselyyellow,flocculentprecipitateseparatesfromthepyridineandtheviscosityofthemixtureincreases.Whentheadditioniscomplete,themixtureisallowedtowarmslowlytoroomtemperaturewithstirring.Withinonehourtheviscosityofthemixturedecreasesandtheinitiallyyellowproductchangestoadeepred,macrocrystallineformthatsettlestothebottomoftheflaskwhenstirringisdiscontinued.Thesupernatantpyridineisdecantedfromthecomplexandthecrystalsarewashedseveraltimesbydecantationwith250-ml.portionsofanhydrouspetroleumether.Theproductiscollectedbyfiltrationonasinteredglassfunnelandwashedwithanhydrouspetroleumether,avoidingcontactwiththeatmosphereasmuchaspossible.Thecomplexisdriedat10mm.untilitisfree-flowing,《药物合成反应》（第三版）闻韧主编第六章氧化反应习题及答案6leaving150–160g.(85–91%)ofdipyridinechromium(VI)oxide3asredcrystals.Theproductisextremelyhygroscopic;contactwithmoistureconvertsitrapidlytotheyellowdipyridiniumdichromate.4Itisstoredat0°inabrownbottle(Note6).(2)Generaloxidationprocedureforalcohols.Asufficientquantityofa5%solutionofdipyridinechromium(VI)oxide(Note1)inanhydrousdichloromethane(Note7)ispreparedtoprovideasixfoldmolarratioofcomplextoalcohol,anexcessusuallyrequiredforcompleteoxidationtothealdehyde.Thefreshlyprepared,purecomplexdissolvescompletelyindichloromethaneat25°at5%concentration,givingadeepredsolution,butsolutionsusuallycontainsmallamountsofbrown,insolublematerialwhenpreparedfromcrudecomplex(Note8).Thealcohol,eitherpureorasasolutioninanhydrousdichloromethane,isaddedtotheredsolutioninoneportionwithstirringatroomtemperatureorlower.Theoxidationofunhinderedprimary(andsecondary)alcoholsproceedstocompletionwithin5to15minutesat25°withdepositionofbrownish-black,polymeric,reducedchromium–pyridineproducts(Note9).Whendepositionofreducedchromiumcompoundsiscomplete(monitoringthereactionbyGCorTLCishelpful),thesupernatantliquidisdecantedfromthe(usuallytarry)precipitate,whichisrinsedthoroughlywithdichloromethane(Note10).Thecombineddichloromethanesolutionsmaybewashedwithdilutehydrochloricacid,sodiumhydrogencarbonatesolution,andwater,orfiltereddirectlythroughafilteraid,orpassedthroughachromatographiccolumntoremovetracesofpyridineandchromiumsalts.Theproductisobtainedbyremovalofdichloromethane;anypyridinethatremainscanoftenberemovedunderreducedpressure.(3)Heptanal.Adry,1-l.three-neckedround-bottomedflaskisequippedwithamechanicalstirrer,and650ml.ofanhydrousdichloromethane(Note7)isadded.Stirringisbegunand77.5g.(0.300mole)ofdipyridinechromium(VI)oxide(Note1)isaddedatroomtemperature,followedby5.8g.(0.050mole)of1-heptanol(Note11)inoneportion.Afterstirringfor20minutes,thesupernatantsolutionisdecantedfromtheinsolublebrowngum,whichiswashedwiththree100-ml.portionsofether.Theetheranddichloromethanesolutionsarecombinedandwashedsuccessivelywith300ml.ofaqueous5%sodiumhydroxide,100ml.of5%hydrochloricacid(Note12),two100-ml.portionsofsaturateda