药物合成反应(第三版闻韧)课后答案Chapter1HalogenationReaction

1、 OO(17)EtOO(18)H=CCI4,70oC42Br2,PBr3(Cat.)-100oC1.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(1)(CH丄NCH2CH2C1HC19Cl(3)(CH丄CHBrCOBr(4)(5)Brch3ch2ch2ch2chcoci(6)(7)EMeMeSO打Br打H恥汇”XhMepH)MeOMe与参考答案不符！(18)BrBr2.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。(1)CH3CH2CH2CH2CHCHCH3ch3ch2ch2chchCHCH3Br(2)COOHBr(3)Brn

2、h2BrOHBr(4)(7)(8)(9)(5)CH2(1)CH3CH2CH2CH2CHCHCH3ch3ch2ch2chchCHCH3Br(2)COOHBr(3)Brnh2BrOHBr(4)(7)(8)(9)(5)CH2CH2CH2BrBrCHCH_CH_BrO(6)(CH3)3CCH2Br(CH3)3CCH2OHOBocHN*BocHNBrBrBrBr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NBS/(PhCO)2O,CCl4,Br2/HgO/tetrachloroethane1.NaNO2,HC1,H2O;2.HPF6；3.(168C

3、)Ph3P,Br2,CH3CN,(200-340C)NBS/(PhCO)2O,CCl4NaI,acetone,refluxing(10min.)Bu3P,Br2,DMFNBS/hv,CCl4NBS/(PhCO)2O,CCl4,reflux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)。Theapparatusconsistsofa1-l.three-neckedflaskequippedwithacondenser,adroppingfunnel,andastirrerterminatinginast

4、iff,crescent-shapedTeflonpolytetrafluoroethylenepaddle.Thestirrermotormusthavegoodtorque(Note1).Theassembledapparatus,whichisprotectedfrommoisturebymeansofdryingtubesinthecondenserandfunnel,ispreferablypredried.About216-224g.(1.62-1.68moles)ofpowderedanhydrousaluminumchlorideisaddedtotheapparatuswit

5、haslittleexposuretothemoistureoftheairaspossible(Note2).Whilethefree-flowingcatalystisstirred(Note3),81g.(0.67mole)ofacetophenoneisaddedfromthedroppingfunnelinaslowstreamoveraperiodof20-30minutes.Considerableheatisevolved,and,ifthedropsofketonearenotdispersed,darkeningorcharringoccurs.Whenaboutone-t

6、hirdoftheacetophenonehasbeenadded,themixturebecomesaviscousball-likemassthatisdifficulttostir.Turningofthestirrerbyhandormorerapidadditionofketoneisnecessaryatthispoint.Theadditionofketone,however,shouldnotbesorapidastoproduceatemperatureabove180.Neartheendoftheaddition,themassbecomesmoltenandcanbes

7、tirredeasilywithoutbeingeitherheatedorcooled.Themoltenmass,inwhichtheacetophenoneiscomplexedwithaluminumchloride,rangesincolorfromtantobrown.Bromine(128g.,0.80mole)isaddeddropwisetothewell-stirredmixtureoveraperiodof40minutes(Note4).Afterallthebrominehasbeenadded,themoltenmixtureisstirredat80-85onas

8、teambathfor1hour,oruntilitsolidifiesifthathappensfirst(Note5).Thecomplexisaddedinportionstoawell-stirredmixtureof1.3l.ofcrackediceand100ml.ofconcentratedhydrochloricacidina2-l.beaker(Note6).Partofthecoldaqueouslayerisaddedtothereactionflasktodecomposewhateverpartofthereactionmixtureremainsthere,andt

9、heresultingmixtureisaddedtothebeaker.Thedarkoilthatsettlesoutisextractedfromthemixturewithfour150-ml.portionsofether.Theextractsarecombined,washedconsecutivelywith100ml.ofwaterand100ml.of5%aqueoussodiumbicarbonatesolution,driedwithanhydroussodiumsulfate,andtransferredtoashort-neckeddistillationflask

10、.Theetherisremovedbydistillationatatmosphericpressure,andcrude3-bromoacetophenoneisstrippedfromafewgramsofheavydarkresiduebydistillationatreducedpressure.Thecolorlessdistillateiscarefullyfractionatedinacolumn20cm.longand1.5cm.indiameterthatisfilledwithCarborundumorHeli-Pakfilling.Thecombinedmiddlefractionsofconstantrefractiveindexaretakenas3-bromoacetophenone；weight,94-100g.(70-75%