./1、About216–224g.<1.62–1.68moles>ofpowderedanhydrousaluminumchlorideisaddedtoa1Lthree-neckedflask.在1L的三口燒瓶中加入大約216-224g<1.62–1.68moles>的無水三氯化鋁。Whilethefree-flowingcatalystisstirred<Note3>,81g.<0.67mole>ofacetophenoneisaddedfromthedroppingfunnelinaslowstreamoveraperiodof20–30minutes.自由流動的催化劑邊攪拌邊用滴液漏斗緩慢滴加81g苯乙酰。Considerableheatisevolved,and,ifthedropsofketonearenotdispersed,darkeningorcharringoccurs.放熱反應,假如滴加的酮不能被分散,就會變黑或是碳化。Whenaboutone-thirdoftheacetophenonehasbeenadded,themixturebecomesaviscousball-likemassthatisdifficulttostir.當三分之一的乙酰苯被滴加,反應混合物變成一個很難攪拌的粘性的球狀團塊。Turningofthestirrerbyhandormorerapidadditionofketoneisnecessaryatthispoint.在這時,改用手動攪拌或快速滴加酮是非常必要的。Theadditionofketone,however,shouldnotbesorapidastoproduceatemperatureabove180°.然而,速度不能太快,當反應溫度超過180℃時。Neartheendoftheaddition,themassbecomesmoltenandcanbestirredeasilywithoutbeingeitherheatedorcooled.Themoltenmass,inwhichtheacetophenoneiscomplexedwithaluminumchloride,rangesincolorfromtantobrown.當快滴加完時,團塊開始融化,表明苯乙酰已經和三氯化鋁混合完全,顏色也逐漸從黃褐色變為棕色。Bromine<128g.,0.80mole>isaddeddropwisetothewell-stirredmixtureoveraperiodof40minutes<Note4>.在40分鐘內在攪拌下把溴緩慢滴加到混合物中。Afterallthebrominehasbeenadded,themoltenmixtureisstirredat80–85°onasteambathfor1hour.溴滴加完后,熔融混合物在80-85℃蒸氣浴下攪拌1小時。Thecomplexisaddedinportionstoawell-stirredmixtureof1.3l.ofcrackediceand100ml.ofconcentratedhydrochloricacidina2-l.beaker<Note6>.反應物加入到1.3L碎冰和100ml濃鹽酸的混合物中在2L的燒杯中混合均勻。Partofthecoldaqueouslayerisaddedtothereactionflasktodecomposewhateverpartofthereactionmixtureremainsthere,andtheresultingmixtureisaddedtothebeaker.把部分的冰水層加入到燒瓶中洗滌殘留物,然后合并到燒杯中。Thedarkoilthatsettlesoutisextractedfromthemixturewithfour150-ml.portionsofether分四次把深色的油從混合物中用150ml萃取出來。Theextractsarecombined,washedconsecutivelywith100ml.ofwaterand100ml.of5%aqueoussodiumbicarbonatesolution,driedwithanhydroussodiumsulfate,andtransferredtoashort-neckeddistillationflask.合并萃取液,用100ml水和100ml5%的小蘇打洗滌,用無水硫酸鈉干燥。Theetherisremovedbydistillationatatmosphericpressure,andcrude3-bromoacetophenoneisstrippedfromafewgramsofheavydarkresiduebydistillationatreducedpressure.乙醚在常壓下蒸餾,微量的溴苯乙酮通過減壓蒸餾的方法從大量深色殘渣中被分離出來。Thecolorlessdistillateiscarefullyfractionatedtoobtain94–100g.通過分餾,得到無色的流出液94-100g2、反應式：3、2-Methyl-4-ethoxalylcyclopentane-1,3,5-trione.Asolutionofsodiumethoxideispreparedina2-l.three-necked,round-bottomedflaskfittedwithamercury-sealedstirrer,arefluxcondensercarryingadryingtube,andastopperbytheadditionof69.0g.<3moles>ofsodiumto950ml.ofabsoluteethanol.69.0g〔3mol鈉和950ml無水乙醇在配有干燥回流冷凝管和汞封攪拌器的2L三口圓底燒瓶中制備乙醇鈉。Thesolutioniscooledto0–5°inanicebathandstirred.溶液在0-5℃下冰浴攪拌。Thestopperisreplacedbyadroppingfunnel,andacoldmixture<5–15°>of108g.<1.50moles>offreshlydistilled2-butanoneand482g.<3.30moles>ofdiethyloxalate<Note1>isaddedgraduallyoveraperiodof30minutes.瓶塞用分液漏斗取代,108g〔1.5mol的丁二酮和482g〔3.3mol的乙二酸二乙酯在5-15℃下低溫混合,在30分鐘內逐步滴加到溶液中。Aftertheadditioniscomplete,thethick,orange-redmixtureisallowedtowarmwithcontinuedstirringtoroomtemperature,heatedunderrefluxfor30minutes,andcooledagainto0°inanicebath.完全加入后,橘紅色的粘稠物繼續攪拌至室溫,加熱回流30分鐘后在冰浴中冷卻至0℃。Themixtureisdecomposedbystirringwith165ml.ofsulfuricacid<1:1byvolume>addedinportions.將165ml濃硫酸〔體積比1:1在攪拌加入,分解混合物。Thesodiumsulfateformedisfilteredbysuctionandwashedwithethanol<150–200ml.><Note2>.硫酸鈉抽濾后用乙醇〔150–200ml洗滌。Thewashingsandfiltratearecombinedandconcentratedbyevaporation.合并濾液和洗滌液后蒸發濃縮。Theyellowishbrownproductwhichaccumulatesbyslowcrystallizationiscollectedbyfiltration,washedwithsmallquantitiesofice-coldwater,anddriedinair.過濾緩慢析出的棕黃色產品用小劑量的冰水洗滌后在空氣中干燥。Thecrudeproductweighs140–150g.粗產品140-150g。Furtherevaporativeconcentrationofthemotherliquorfollowedbycoolingfurnishesanadditional40–50g.oftheketoester,此外將母液用冷凍蒸發濃縮后又得到40-50g的酮酯。bringingthetotalyieldto180–200g.<53–59%>產品總共180-200g〔產率53-59%<Note2>.Thiscrudematerial<m.p.120–130°>isusedinthenextstep.粗品〔熔點120–130℃用于下一步中ApuresamplecanbeobtainedbycrystallizationfromethylacetateaftertreatmentwithNoritactivatedcarbon,m.p.160–162°.純品是經過活性炭處理后在乙酸乙酯中結晶得到,熔點160–162℃。Theprocedurefor2-pyrrolealdehyde2-吡咯甲醛Ina3-l.three-neckedround-bottomedflask,fittedwithasealedstirrer,adroppingfunnel,andarefluxcondenser,isplaced80g.<1.1moles>ofdimethylformamide<Note1>.在配有封閉攪拌器、滴液漏斗和冷凝回流裝置的三口圓底燒瓶中放入80g〔1.1mol的二甲基甲酰胺。Theflaskisimmersedinanicebath,andtheinternaltemperatureismaintainedat10–20°,while169g.<1.1moles>ofphosphorusoxychlorideisaddedthroughthedroppingfunneloveraperiodof15minutes.燒瓶浸入冰浴中,內部溫度保持在10-20℃,169g〔1.1mol的磷酰氯通過滴液漏斗在15分鐘內滴加。Anexothermicreactionoccurswiththeformationofthephosphorusoxychloride-dimethylformamidecomplex.放熱反應生成磷酰氯二甲基甲酰胺化合物。Theicebathisremoved,andthemixtureisstirredfor15minutes<Note2>.移去冰浴,在攪拌15分鐘。Theicebathisreplaced,and250ml.ofethylenedichlorideisaddedtothemixture.重新再冰浴下加入250ml的二氯乙烯。Whentheinternaltemperaturehasbeenloweredto5°,asolutionof67g.<1.0mole>offreshlydistilledpyrrolein250ml.ofethylenedichlorideisaddedthroughacleandroppingfunneltothestirred,cooledmixtureoveraperiodof1hour.當內部溫度降到5度時,把67g〔1.0mol新蒸餾的吡咯加入到250二氯乙烯中,通過滴液漏斗在1小時內低溫下邊攪拌邊滴加。Aftertheadditioniscomplete,theicebathisreplacedwithaheatingmantle,andthemixtureisstirredattherefluxtemperaturefor15minutes,duringwhichtimethereiscopiousevolutionofhydrogenchloride.滴加完后,用加熱裝置取代冰浴,攪拌回流15分鐘,直到有大量氯化氫產生。Themixtureisthencooledto25–30°,andtoitisaddedthroughthedroppingfunnelasolutionof750g.<5.5moles>ofsodiumacetatetrihydrate<Note3>inaboutofwater,cautiouslyatfirst,thenasrapidlyaspossible.當混合物降溫到25-30℃后,通過滴液漏斗加入750g〔5.5mol的三水醋酸鈉溶液,開始要小心,然后要盡可能地快。Thereactionmixtureisagainrefluxedfor15minutes,vigorousstirringbeingmaintainedallthewhile<Note4>.反應物在充分攪拌下重新回流15分鐘。Thecooledmixtureistransferredtoa3-l.separatoryfunnel,andtheethylenedichloridelayerisremoved.冷卻的混合物轉移到分液漏斗中,出去二氯乙烯層。Theaqueousphaseisextractedthreetimeswithatotalofabout500ml.ofether.水相用500ml乙醚分三次萃取。Theetherandethylenechloridesolutionsarecombinedandwashedwiththree100-ml.portionsofsaturatedaqueoussodiumcarbonatesolution,whichisaddedcautiouslyatfirsttoavoidtoorapidevolutionofcarbondioxide.合并乙醚和氯乙烯溶液,用100ml飽和碳酸鈉溶液分三次洗滌,然后通入二氧化碳,通入時要小心不要太快。Thenon-aqueoussolutionisthendriedoveranhydroussodiumcarbonate,thesolventsaredistilled,andtheremainingliquidistransferredtoaClaisenflaskanddistilledfromanoilbathunderreducedpressure<Note5>.非水溶液用無水碳酸鈉干燥,蒸餾溶劑,余下的溶液移入克氏燒瓶在油浴中減壓蒸餾。Thealdehydeboilsat78°at2mm.;thereisverylittlefore-runandverylittleresidue.醛沸點78度在2mm；很少有預留無和殘渣。Theyieldofcrude2-pyrrolealdehydeis85–90g.<89–95%>,asanalmostwater-whiteliquidwhichsooncrystallizes.當幾乎透明的液體會馬上結晶,粗品產量85-90g〔89-95%。Asampledriedonaclayplatemeltsat35–40°.樣品在素燒瓷板上干燥,熔點35-40度。Thecrudeproductispurifiedbydissolvinginboilingpetroleumether<b.p.40–60°>,intheratioof1g.ofcrude2-pyrrolealdehydeto25ml.ofsolvent,andcoolingthesolutionslowlytoroomtemperature,followedbyrefrigerationforafewhours.粗品溶解在沸騰的石油醚中〔沸點40-60度,一克粗品2-甲基吡啶加入25ml溶劑,在室溫下冷卻,這后再冷凍數小時。Thepurealdehydeisobtainedfromthecrudeinapproximately85%recovery.純品醛是從粗品中得到,收率85%。Theover-allyieldfrompyrroleis78–79%ofpure2-pyrrolealdehyde,m.p.44–45°.總得率為78-79%熔點44-45度。〔1反應式4、<1>Ina3L.round-bottomedflask<Note1>fittedwitharefluxcondenserareplaced625cc.of95percentalcohol<Note2>,500cc.ofwater,500g.<476cc.,4.7moles>ofpurebenzaldehyde<Note3>,and50g.ofsodiumcyanide<96–98percent>.在配有回流冷凝器的3L圓底燒瓶中加入625ml的95%酒精、500ml水、500g〔476ml,4,7mol的苯甲醛和50g96-98%的氰化鈉。Themixtureisthenheatedandkeptboilingforone-halfhour<Note4>.混合物加熱并保持沸騰1.5小時。Inthecourseofabouttwentyminutes,crystalsbegintoseparatefromthehotsolution.在20分鐘后晶體開始從熱溶液中析出。Attheendofthethirtyminutes,thesolutioniscooled,filteredwithsuction,andwashedwithalittlewater.在最后的30分鐘,冷卻溶液,抽濾并用少量水洗滌Theyieldofdrycrudebenzoin,whichiswhiteorlightyellow,is450–460g.有450-460g白色或亮黃色的干燥的安息香。<90–92percentofthetheoreticalamount>.理論產率90-92%。Inordertoobtainitcompletelypure,thecrudesubstanceisrecrystallizedfrom95percentalcohol,90g.ofcrudematerialbeingdissolvedinabout700cc.ofboilingalcohol;uponcooling,ayieldof83g.ofwhite,purebenzoinwhichmeltsat129°isobtained.為了得到純度高的產品,粗產品要在酒精中重結晶,90g粗品溶解在700ml沸騰的酒精中,冷卻,得到83g熔點為129攝氏度的白色安息香純品。<2>Ina1L.three-neckedround-bottomedflaskequippedwithamechanicalstirrer,shortrefluxcondenser,andbentglasstubereachingbelowthesurfaceoftheliquidfortheintroductionofhydrogenchloride,areplaced50g.<0.36mole>ofp-nitrophenol<Note1>,650ml.ofconcentratedhydrochloricacid,5ml.ofconcentratedsulfuricacid<Note2>,and76g.<1mole>ofmethylal<Note3>.在配有機械攪拌,短期冷凝回流器和一個為的是深入液面下通氯化氫氣體的彎曲的玻璃管三口圓底燒瓶中加入50g〔0.36mol對硝基苯酚,650ml的濃鹽酸,5ml的濃硫酸和76g〔1mol的二甲氧基甲烷。Themixtureisstirredwhilethetemperatureismaintainedat70±2°for4–5hoursbymeansofawaterbath<Note4>.在水浴中保持70±2度攪拌4-5小時。Duringthistimehydrogenchlorideisbubbledintothereactionmixturethroughthebentglasstube,andtheexcessgasiscarriedawaythroughtherefluxcondensertoahoodorgas-absorptiontrap<Note5>.在此期間通過玻璃彎管把氯化氫氣體通入反應混合物中,過量的氣體被帶到回流冷凝器被氣體吸收罩吸收。The2-hydroxyl-5-nitrobenzylchloridebeginstoseparateasasolidabout1hourafterthebeginningofthereaction.在反應開始后的一個小時,2-羥基-5-硝基苯氯化物作為固體被分離。Attheendthemixtureiscooledinicefor1hourwherebymorecrystalsseparate,afterwhichtheacidliquorsareeitherfilteredordecantedfromthecrystals<Note6>.最后把混合物在冰中冷卻1小時,使更多的晶體析出,之后把酸性液體過濾或傾析得到晶體。The2-hydroxy-5-nitrobenzylchlorideispurifiedbyrecrystallizationfrom125ml.ofhotbenzene2-羥基-5-硝基苯氯化物在熱的苯中重結晶純化。<Note7>.Theyieldis46g.<69%basedonp-nitrophenol>ofawhiteproductmeltingat129–130°.白色產物46g〔對硝基苯酚含69%熔點129-130度5、B.Benzyltrans-1,3-butadiene-1-carbamate.A

dry,1-l.,three-necked,round-bottomedflaskisequippedwithamagneticstirringbar,athermometer,anda250-ml.,pressure-equalizingdroppingfunnelbearinganitrogeninlet.Theflaskisflushedwithnitrogenandchargedwith

49g.<0.50mole>of

trans-2,4-pentadienoicacid,

80g.<0.62mole>of

N,N-diisopropylethylamine,and

300ml.of

acetone<Note6>.Theresultingsolutionisstirredandcooledto0°inan

ice–saltbath.Asolutionof

55g.<0.51mole>of

ethylchloroformatein

150ml.of

acetoneisaddedover30minuteswhilethetemperatureismaintainedbelow0°<Note7>.Stirringiscontinuedforanadditional30minutesat0°,afterwhichachilledsolutionof

65g.<1.0mole>of

sodiumazide<Note8>in170ml.ofwaterisaddedovera20-minuteinterval,keepingthetemperaturebelow0°.Thecontentsoftheflaskarestirredforanadditional10–15minutesat0°<Note9>andpouredintoa

2-l.separatoryfunnelcontaining500ml.ofice-water.Theacylazideisisolatedbyextractionwithsix

250-ml.portionsof

toluene.Thecombinedtolueneextractsaredriedover

anhydrous

magnesiumsulfatefor20minutesandconcentratedtoavolumeofca.300ml.onarotaryevaporatoratawaterbathtemperatureof40–50°<Note10>.Caution!Theacylazideispotentiallyexplosive.Thesolutionshouldnotbeevaporatedtodryness.Whilethetoluenesolutionisbeingconcentrated,a

dry,2-l.,three-necked,round-bottomedflaskequippedwithamechanicalstirrer,a500-ml.pressure-equalizingdroppingfunnel,asimpledistillationhead,andaheatingmantle

ischargedwith

43g.<0.40mole>ofbenzylalcohol,

250mg.of

4-tert-butylcatechol<Note11>,and

200ml.of

toluene.About30ml.oftouleneisdistilledfromtheflasktoremovetraceamountsofwater,andthedistillationheadisreplacedwithacondenserfittedwithanitrogeninlet.Thetoluenesolutionisstirredandheatedatarapidrefluxunderanitrogenatmosphereasthetoluenesolutionoftheacylazideisaddedover30minutes.ThedisappearanceoftheacylazideandisocyanateisfollowedbyIRanalysis<Note12>.Conversiontothecarbamateiscompletein10–30minutes,afterwhichthesolutioniscooledrapidlytoroomtemperaturebyimmersingtheflaskinan

icebath.Thetolueneisrapidlyremovedonarotaryevaporatorwiththewaterbathat40–50°,producingayellowsolidresidue<Note13>whichisdissolvedin

50ml.of95%

ethanolandallowedtocrystall