药物合成反应闻韧第三版课后翻译

1、实用标准文案1、About 216 224 g. (1.62 1.68 moles) of powdered anhydrous aluminum chloride isadded to a 1Lthree-necked flask.在 1L 的三口烧瓶中加入大约216-224g(1.62 1.68 moles)的无水三氯化铝。 Whilethe free-flowingcatalyst is stirred(Note 3), 81 g. (0.67mole)of acetophenone is added from the dropping funnel in a slow stream o

2、ver a period of 20 30 minutes.自由流动的催化剂边搅拌边用滴液漏斗缓慢滴加81g 苯乙酰。Considerableheatis evolved,and, if the dropsof ketoneare not dispersed, darkening or charring occurs.放热反应，假如滴加的酮不能被分散，就会变黑或是碳化。When about one-third of theacetophenone has been added, the mixture becomes a viscous ball-like mass that isdiffic

3、ulttostir. 当三分之一的乙酰苯被滴加，反应混合物变成一个很难搅拌的粘性的球状团块。 Turning of the stirrer by hand or more rapid addition of ketone is necessary atthis point.在这时，改用手动搅拌或快速滴加酮是非常必要的。The addition of ketone,however, should not be so rapid as to produce a temperature above 180 . 然而，速度不能太快，当反应温度超过180时。 Near the end of theadd

4、ition, the mass becomes moltenand can be stirred easily without being either heated or cooled. The molten mass, inwhich the acetophenone is complexed with aluminum chloride, ranges in color from tanto brown.当快滴加完时，团块开始融化，表明苯乙酰已经和三氯化铝混合完全，颜色也逐渐从黄褐色变为棕色。Bromine (128 g., 0.80 mole) is added dropwise to

5、 the well-stirred mixture over aperiod of 40 minutes (Note 4). 在 40分钟内在搅拌下把溴缓慢滴加到混合物中。After all thebromine has been added, the molten mixture is stirred at 80 85 on a steam bath for1 hour.溴滴加完后，熔融混合物在80-85 蒸气浴下搅拌 1 小时。 The complex is added inportionstoa well-stirredmixtureof 1.3 l. of cracked iceand

6、 100 ml.of concentratedhydrochloric acid in a 2-l. beaker (Note 6).反应物加入到1.3L 碎冰和 100ml 浓盐酸的混合物中在2L 的烧杯中混合均匀。 Part of the cold aqueous layer is added to the reactionflask todecompose whateverpartofthe reaction mixture remains there, and the resultingmixture is added to the beaker.把部分的冰水层加入到烧瓶中洗涤残留物，

7、然后合并到烧杯中。 Thedarkoil that settlesout isextracted from the mixture withfour150-ml. portionsof ether分四次把深色的油从混合物中用150ml 萃取出来。 The extractsarecombined, washedconsecutivelywith 100 ml. of waterand 100 ml. of 5% aqueous sodium bicarbonate solution,dried with anhydrous sodium sulfate, and transferred to a

8、 short-necked distillationflask.合并萃取液，用 100ml 水和 100ml 5%的小苏打洗涤，用无水硫酸钠干燥。The ether isremoved by distillation at atmospheric pressure, and crude 3-bromoacetophenone isstripped from a few grams of heavy dark residue by distillation at reduced pressure.精彩文档实用标准文案乙醚在常压下蒸馏，微量的溴苯乙酮通过减压蒸馏的方法从大量深色残渣中被分离出来。T

9、hecolorless distillate is carefully fractionated to obtain 94 100 g. 通过分馏，得到无色的流出液94-100g2、精彩文档实用标准文案精彩文档实用标准文案反应式：3、2-Methyl-4-ethoxalylcyclopentane-1,3,5-trione. A solution of sodium ethoxide is prepared in a 2-l. three-necked, round-bottomed flask fitted with a mercury-sealed stirrer, a reflux co

10、ndenser carrying a drying tube, and a stopper by the addition of69.0 g. (3 moles) of sodium to 950 ml. of absolute ethanol. 69.0g（ 3mol ）钠和 950ml无水乙醇在配有干燥回流冷凝管和汞封搅拌器的2L 三口圆底烧瓶中制备乙醇钠。The solutionis cooled to 0 5 in an ice bath andstirred.溶液在 0-5 下冰浴搅拌。The stopper isreplaced by a dropping funnel, and

11、a cold mixture (5 15 ) of 108 g. (1.50 moles) offreshly distilled2-butanoneand 482 g.(3.30moles) of diethyl oxalate (Note1)isaddedgradually over a period of 30 minutes.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 下低温混合，在30 分钟内逐步滴加到溶液中。Afterthe additioniscomplete, the thick, orange-redmixt

12、ure is allowed to warm withcontinuedstirring to room temperature, heated under reflux for 30 minutes, and cooled again to0 in an ice bath.完全加入后，橘红色的粘稠物继续搅拌至室温，加热回流30分钟后在冰浴中冷却至 0。 The mixtureisdecomposed by stirringwith165 ml. of sulfuricacid(1:1by volume) added in portions.将 165ml 浓硫酸（体积比1:1 ）在搅拌加入，

13、分解混合物。Thesodium sulfateformed is filteredby suction and washed withethanol (150 200 ml.)(Note精彩文档实用标准文案2). 硫酸钠抽滤后用乙醇（150 200 ml）洗涤。 The washingsand filtrateare combined andconcentrated by evaporation .合并滤液和洗涤液后蒸发浓缩。The yellowish brown productwhich accumulates by slow crystallizationis collected by f

14、iltration,washed with smallquantities of ice-cold water, and dried in air.过滤缓慢析出的棕黄色产品用小剂量的冰水洗涤后在空气中干燥。The crude product weighs 140 150 g. 粗产品 140-150g 。 Furtherevaporative concentration of the mother liquor followed by cooling furnishes anadditional 40 50 g. of the keto ester,此外将母液用冷冻蒸发浓缩后又得到40-50g

15、 的酮酯。 bringing the total yield to 180 200 g. (53 59%)产品总共 180-200g（产率 53-59%）(Note 2). This crude material (m.p. 120 130 ) is used in the next step.粗品（熔点120 130 ）用于下一步中 A pure sample can be obtained by crystallization from ethylacetate after treatment with Norit activated carbon, m.p. 160 162 . 纯品是经

16、过活性炭处理后在乙酸乙酯中结晶得到，熔点160 162。The procedure for 2- pyrrolealdehyde 2-吡咯甲醛In a 3-l. three-necked round-bottomed flask, fitted with a sealed stirrer, adroppingfunnel,and arefluxcondenser,is placed80g.(1.1moles)ofdimethylformamide (Note 1).在配有封闭搅拌器、滴液漏斗和冷凝回流装置的三口圆底烧瓶中放入 80g（ 1.1mol ）的二甲基甲酰胺。The flask isi

17、mmersed inan ice bath,and theinternaltemperature ismaintainedat 10 20 ,while169g.(1.1moles)ofphosphorus oxychloride is added through the dropping funnel over a period of 15minutes.烧瓶浸入冰浴中，内部温度保持在10-20 ， 169g（ 1.1mol ）的磷酰氯通过滴液漏斗在 15分钟内滴加。 An exothermic reaction occurswiththe formation of the phosphor

18、usoxychloride - dimethylformamide complex.放热反应生成磷酰氯二甲基甲酰胺化合物。The ice bath is removed, and the mixture is stirred for 15 minutes (Note 2).移去冰浴，在搅拌 15分钟。The ice bath is replaced, and 250 ml. of ethylene dichloride is added to themixture.重新再冰浴下加入250ml 的二氯乙烯。 When the internal temperature has beenlowere

19、d to 5 , a solution of 67 g. (1.0 mole) of freshly distilled pyrrole in 250ml. of ethylene dichlorideis added througha cleandropping funnelto the stirred,cooled mixture over a period of 1 hour.当内部温度降到 5度时，把 67g（1.0mol ）新蒸馏的吡咯加入到 250二氯乙烯中，通过滴液漏斗在1小时内低温下边搅拌边滴加。After theadditionis complete, theice bath

20、is replacedwith a heating mantle,and themixtureis stirred at the reflux temperature for 15 minutes, during which time there iscopious evolution of hydrogen chloride.滴加完后，用加热装置取代冰浴，搅拌回流15分钟， 直到有大量氯化氢产生。The mixture is then cooledto 25 30 , and toitis added throughthedroppingfunnela solution of 750 g.

21、(5.5 moles) of sodium acetate trihydrate (Note 3) in about ofwater, cautiously atfirst,then as rapidlyas possible.当混合物降温到 25-30 后，通过滴液漏斗加入750g（ 5.5mol ）的三水醋酸钠溶液， 开始要小心， 然后要尽可能地快。 Thereactionmixtureis again refluxedfor15minutes,vigorousstirringbeing精彩文档实用标准文案maintained all the while (Note 4).反应物在充分搅拌

22、下重新回流15分钟。The cooled mixture istransferredto a 3-l.separatoryfunnel, and theethylenedichloride layer is removed.冷却的混合物转移到分液漏斗中，出去二氯乙烯层。Theaqueous phase is extracted three times with a total of about 500 ml. of ether.水相用 500ml 乙醚分三次萃取。 The ether and ethylene chloride solutions are combinedand washed

23、with three 100-ml. portions of saturated aqueous sodium carbonatesolution,which is added cautiouslyatfirsttoavoid too rapidevolutionof carbondioxide.合并乙醚和氯乙烯溶液， 用 100ml饱和碳酸钠溶液分三次洗涤，然后通入二氧化碳，通入时要小心不要太快。 The non-aqueous solutionisthen dried over anhydrous sodiumcarbonate, the solvents are distilled, a

24、nd the remaining liquid is transferred toa Claisen flask and distilled from an oilbathunder reduced pressure (Note 5).非水溶液用无水碳酸钠干燥，蒸馏溶剂，余下的溶液移入克氏烧瓶在油浴中减压蒸馏。Thealdehyde boils at 78 at2 mm.; thereisverylittlefore-runand verylittleresidue.醛沸点 78 度在 2mm；很少有预留无和残渣。The yield of crude2-pyrrolealdehyde is 8

25、590 g. (89 95%), as an almost water-white liquid which soon crystallizes.当几乎透明的液体会马上结晶，粗品产量85-90g （ 89-95%）。 A sample dried ona clay platemelts at35 40 . 样品在素烧瓷板上干燥， 熔点 35-40度。The crudeproduct ispurifiedby dissolving in boiling petroleum ether (b.p. 40 60 ), in the ratio of 1 g. ofcrude 2-pyrroleald

26、ehyde to 25 ml. of solvent, and cooling the solution slowly toroom temperature, followed by refrigeration for a few hours.粗品溶解在沸腾的石油醚中（沸点 40-60 度），一克粗品2- 甲基吡啶加入25ml 溶剂，在室温下冷却，这后再冷冻数小时。 The pure aldehyde is obtained from thecrude in approximately85% recovery.纯品醛是从粗品中得到，收率85%。 The over-allyieldfrom py

27、rroleis78 79%ofpure2-pyrrolealdehyde, m.p. 44 45 . 总得率为78-79%熔点 44-45 度。（1）反应式精彩文档实用标准文案4、(1)Ina 3L. round-bottomedflask(Note 1) fitted witha reflux condenserare placed625 cc. of 95 per cent alcohol (Note 2), 500 cc. of water, 500 g. (476 cc., 4.7 moles)of pure benzaldehyde (Note 3), and 50 g. of so

28、dium cyanide (96 98 per cent).在配有回流冷凝器的 3L 圆底烧瓶中加入625ml 的 95%酒精、 500ml 水、 500g（ 476ml ， 4,7mol ）的苯甲醛和 50g 96-98% 的氰化钠。 The mixture is then heated and kept boiling for one-half hour(Note4).混合物加热并保持沸腾1.5 小时。 In the course ofabout twenty minutes,crystalsbegintoseparate from the hot solution.在 20 分钟后晶体开

29、始从热溶液中析出。At the end精彩文档实用标准文案of the thirty minutes, the solution is cooled, filtered with suction, and washed witha little water.在最后的 30 分钟，冷却溶液，抽滤并用少量水洗涤The yield of dry crudebenzoin, which is white or light yellow, is 450 460 g. 有 450-460g 白色或亮黄色的干燥的安息香。 (90 92 per cent of the theoretical amount).

30、理论产率 90-92%。 In order toobtain it completelypure, the crude substanceisrecrystallizedfrom 95 per cent alcohol,90 g. of crude materialbeing dissolvedin about700 cc. of boilingalcohol;upon cooling,a yield of 83 g. of white, pure benzoin which melts at 129 is obtained.为了得到纯度高的产品，粗产品要在酒精中重结晶，90g 粗品溶解在 7

31、00ml 沸腾的酒精中， 冷却， 得到 83g熔点为 129 摄氏度的白色安息香纯品。(2)In a 1L.three-necked round-bottomedflask equippedwitha mechanical stirrer,shortreflux condenser, and bent glass tubereaching belowthe surface of the liquidforthe introductionofhydrogenchloride,areplaced50g.(0.36 mole)ofp-nitrophenol(Note 1),650ml.of conc

32、entratedhydrochloricacid,5 ml.ofconcentrated sulfuric acid (Note 2), and 76 g. (1 mole) of methylal (Note 3).在配有机械搅拌， 短期冷凝回流器和一个为的是深入液面下通氯化氢气体的弯曲的玻璃管三口圆底烧瓶中加入50g（ 0.36mol ）对硝基苯酚， 650ml 的浓盐酸， 5ml的浓硫酸和 76g（ 1mol）的二甲氧基甲烷。 The mixture is stirred while the temperature is maintained at 70 2 for 4 5 hours

33、by means of a water bath (Note 4).在水浴中保持70 2度搅拌4-5 小时。 During this time hydrogen chloride is bubbled into the reaction mixturethrough the bent glass tube, and the excess gas is carried away through the refluxcondenser to a hood or gas- absorption trap (Note 5).在此期间通过玻璃弯管把氯化氢气体通入反应混合物中，过量的气体被带到回流冷凝器被

34、气体吸收罩吸收。The 2- hydroxyl-5-nitrobenzylchloride beginstoseparate as a solidabout 1 hourafter the beginning of the reaction.在反应开始后的一个小时，2- 羟基 -5- 硝基苯氯化物作为固体被分离。 At the end the mixture is cooled in ice for 1 hour whereby morecrystals separate,afterwhichthe acid liquorsareeitherfilteredor decanted fromth

35、e crystals (Note 6).最后把混合物在冰中冷却1 小时，使更多的晶体析出，之后把酸性液体过滤或倾析得到晶体。The 2-hydroxy-5-nitrobenzyl chloride is purified byrecrystallization from 125 ml. of hot benzene 2-羟基 -5- 硝基苯氯化物在热的苯中重结晶纯化。 (Note 7).The yield is 46 g. (69% based on p-nitrophenol)of a white productmelting at 129 130 . 白色产物46g（对硝基苯酚含69%）熔

36、点 129-130 度精彩文档实用标准文案5、 B.Benzyltrans-1,3-butadiene -1- carbamate.Adry,1-l.,three-necked,round-bottomedflaskisequippedwithamagneticstirringbar,a thermometer,and a 250-ml.,pressure-equalizingdroppingfunnel bearinga nitrogen inlet. The flask is flushed withnitrogenand charged with49 g. (0.50mole)oftra

37、ns -2,4-pentadienoicacid,80g.(0.62mole)ofN,N-diisopropylethylamine,and300ml.ofacetone(Note 6).Theresultingsolutionisstirredand cooledto0 in anice saltbath.A solutionof55 g.(0.51mole) ofethylchloroformatein150 ml.ofacetoneisadded over 30 minuteswhilethetemperatureismaintainedbelow0 (Note7).Stirringis

38、continuedfor anadditional 30 minutes at 0 , after which a chilled solution of65 g. (1.0 mole)ofsodium azide(Note 8)in 170 ml. of water is added over a 20-minute interval,keepingthetemperaturebelow0 . The contentsof the flaskare stirredforan additional10 15 minutes at 0(Note 9)and poured into a2-l. s

39、eparatory funnelcontaining500 ml.ofice-water.The acylazideisisolatedby extractionwithsix250-ml.portionsoftoluene.Thecombinedtolueneextractsaredriedoveranhydrousmagnesiumsulfatefor 20 minutes and concentrated to a volume ofca. 300 ml. on a rotaryevaporatorata waterbath temperatureof 40 50(Note10).Cau

40、tion!The acylazideis potentially explosive. The solution should not be evaporated to dryness.Whilethetoluenesolutionisbeingconcentrated,adry,2-l.,three-necked,精彩文档实用标准文案round-bottomedflaskequippedwitha mechanical stirrer,a 500-ml.pressure-equalizingdroppingfunnel,a simpledistillationhead,and a heati

41、ng mantleis chargedwith43g.(0.40mole)ofbenzyl alcohol,250 mg. of4- tert -butylcatechol(Note11),and200ml. oftoluene. About 30 ml. of toulene is distilled from the flask to remove traceamounts of water, and the distillation head is replaced with a condenser fitted withanitrogeninlet.Thetoluenesolution

42、isstirredand heatedata rapidrefluxunderanitrogenatmosphere as thetoluenesolution of the acyl azide is added over 30minutes.Thedisappearanceofthe acylazide and isocyanateis followedbyIRanalysis(Note 12). Conversion to the carbamate is complete in 10 30 minutes, afterwhichthe solutioniscooled rapidlyto room temperatureby immersingthe flaskinanicebath. Thetolueneis rapidly removed on a rotary evaporator with the water bath at40 50 , producing a yellow solid residue(Note 13)which is dissolved in50 ml.of 95%ethanoland allowed to crystallize in