药物合成反应闻韧第三版课后翻译.docx

精品名师归纳总结资料word 精心总结归纳 - - - - - - - - - - - -1、About 216224 g. 1.621.68 moles of powdered anhydrous aluminumchloride is added to a 1Lthree-necked flask.在 1L 的三口烧瓶中加入大约216-224g1.621.68 moles的无水三氯化铝。While the free-flowing catalyst is stirred Note 3, 81 g. 0.67 mole of acetophenone is added from the droppingfunnel in a slow stream over a period of 2030 minutes.自由流淌的催化剂边搅拌边用滴液漏斗缓慢滴加81g苯乙酰。Considerable heat is evolved, and, if the drops of 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 the acetophenone has been added, themixture becomes a viscous ball-like mass that is difficult to stir.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 ormore rapid addition of ketone is necessary at this point.在这时，改用手动搅拌或快速滴加酮是特别必要的。The addition of ketone, however, should not be so rapid as toproduce 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 the addition, the mass becomes molten and can be stirred easily without being either heated or cooled. The molten mass, in which the acetophenoneis complexed with aluminum chloride, ranges in color from tan to brown.当快滴加完时，团块开头融解，说明苯乙酰已经和三氯化铝混合完全，颜色也逐步从黄褐色变为棕色。Bromine 128 g., 0.80 mole is added dropwise to the well-stirred mixture overa period 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 the bromine has been added, the molten mixture is stirred at 8085 °on a steambath for 1 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 in portions to a well-stirred mixture of 1.3 l. of cracked ice and 100 ml. ofconcentrated hydrochloric 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 的烧杯中混合匀称。 Part of the cold aqueous layer is added to the reaction flask to decompose whatever part of the reaction mixture remainsthere, and the resulting mixture is added to the beaker.把部分的冰水层加入到烧瓶中洗涤残留物，然后合并到烧杯中。The dark oil that settles out is extracted from themixture with four 150-ml. portions of ether分四次把深色的油从混合物中用150ml萃取出来。 The extracts are combined, washed consecutively with 100 ml. of water and100 ml. of 5% aqueous sodium bicarbonate solution, dried with anhydrous sodiumsulfate, and transferred to a short-necked distillation flask.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 is removed by distillation at atmospheric pressure, and crude 3-bromoacetophenone is stripped from a few可编辑资料 - - - 欢迎下载精品名师归纳总结学习资料 名师精选 - - - - - - - - - -第 1 页，共 10 页 - - - - - - - - - -可编辑资料 - - - 欢迎下载精品名师归纳总结资料word 精心总结归纳 - - - - - - - - - - - -grams of heavy dark residue by distillation at reduced pressure.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别出来。The colorless distillate is carefully fractionated to obtain 94100 g.通过分馏，得到无色的流出液94-100g2、可编辑资料 - - - 欢迎下载精品名师归纳总结学习资料 名师精选 - - - - - - - - - -第 2 页，共 10 页 - - - - - - - - - -可编辑资料 - - - 欢迎下载精品名师归纳总结Preparati on of cvcloDroDane 1. 1- diCarboxylic acid ' ' '-i .f: : 1, 1 -. I:'.'”I 1. To a I -L solution of aqueous 5O6 sodium hvdrgxide, meohanioaIIy sFir tnexJ in a 2-L,three-neck «dflask,wasadded,at25°C,114.Oq0.5molof triethvlbenzvlammon turn chlorideTEBA. C1. .'-.r let. NoLe ZS. 1 L ii”. 5O°A ”: i.'.'”l. i”.i. i .T. ZL ” .“ i. TEBAi . . . 'c'. I I4.DqO.3rnoI“ 23"T ' i.I I iTo Chis vlgomusly sCired suspension was added a mixture of BD.0 q O. 5 molOfand 141.O q 0.75 mol of 1. 2-dibmmoethace all at once. 'r. :' . i 1 .L.- i '.”.'i.”. i -. , .r.ai.:so.oq o.s=oi i:. i .2-. '-.-: i « I o ' - o. rs=oi. :” i :-/ 1mereaction mixture was vigorously stirred for z hr f Note 3J. .-'. '” ' ”/ . I z,'', .-':.-.'.J2-mecontents of the flask were transferred to a # -L ErJenmeyer flaskby rinsing the flask with three 75mL poaons of water. rI”'.-“- "' .”: 'q 'L'. ”' ".- -», 4L : i”i-°.L. II 7SmI:' . l. .'.- :'.” The mlxture was magnetically stirred by dropwlse addition of 1 L of concentrated hydrochloric acld.1-'. ”. lf.'" i'L .". -”.'” . "a4. ft . -. . fThe temperature of the flask was maintained becween 15 and 25°C duringacidification. .i h'.' 1. J * . '.=.i.' -*.' :.'. :”.”. °.- fi- ” 5-z3 r ” ”“ i Imeaqueous laver waspoued nto a 4-L separator funnel and extracted three If mes with 9OO mL Of.*11/. tt .: '4L n »/ ” .b. I' I I Room I1 ” - '. i.The aqueous» ver was saturated with sodium chl oride and extracted th ee times with TOO mL of ether. .: ' . i '' I - -I i''” ”I ' I 500m Ia «. 'I”The ether layers weecombl ned,washed wiCh I L of bnne, dded H_g5O, and decolor1zed with acCl*/ated arggo. ”: i'1. -'L . ' .-:. .-. .l. . ”» .i 'I I . . ' I ”.':- I: I' .Removal of the solvent by rotatg'evaporation gave 55.2 9 of a s«misoIid residue.'J '.'. '-” '”- '* ., ¿ ,- . -” . fi 5.2q i:-. IThe rcsid ue was tri tu ratwdwith 1O0 mL Of benzene. -' ''. I 00m.” :Filt ration of this mixcue gave 63.147.9 g 66736 of 1 as white crystals, mp137 14O”C.-'.-. i.'. .,' ”I -.: 43.-47. 9q ».>”j . i i” , ' .”I : T -u :Prcpurol iiu nd tc iIakJrItjxk I2,1,b- IntneIyI N zohk'hYIc” .-I.n-. I ” .'- ”- - 1 ”l ”i I "AS srIatxin it” 72 ;. IU.dJ n il« it nies/ lene in fi75 ml, t drj. «ic1¿Icie chlrde is plwcdin a I -l. thee-necked tasL equipped'ith o retJux c ndenxer. a stn'er. and a frs pinp tunn«I. 2«rgai1ic layez i w »i'ai«t. aid Ie agieiu4 vi1iiit i4 exlzweS wiil i«” III- i»I. Ixriiiir I-ii ietIi-lens t1tkrik,“.: I ' ''. .-'I . 1, fi1i it 1''- 1 ;- “.r. .' . -Thccaiibiiied rryanic suluiiin is unsled three times w'iili 75-nil. jxriiuns uf' waier. i . 1 I.<t. 7. nd '. 'r. .i. i.'.iA riysIa1 it liydnxjuiii»r ix added 11 lhc titcthjlcric chlorine»pIuTiuft l Nuic a'Iiic ix then tried vei' ml j"tnius a»Iiun su1”ae. J ” ., tc gzvc Ihr rnlctc jwtxtIc1. h,p. 6g7J ' t-9 Inc.I. .-”= z. ; l” -.” I'. f' .'. ”f. ' ' :'-. '.”>H- -II.Omni After rci1i«ci1fazin diere ix iht»inet fD-bh ¿. R I R9.r j f n rxif»J4ets'te. h,. J l ,W I I fi" I 1 1 1 u«.i.«.ou I.ssJx.'- : « i.« n>/ ' x i x''.: ,I”i.nI, . 1 1 ,.i. .' i i. i it :i i » :可编辑资料 - - - 欢迎下载精品名师归纳总结资料word 精心总结归纳 - - - - - - - - - - - -反应式：3、2-Methyl-4-ethoxalylcyclopentane-1,3,5-trione. A solution of sodium ethoxideis prepared in a 2-l. three-necked, round-bottomed flask fitted with amercury-sealed stirrer, a reflux condenser carrying a drying tube, and a stopper by the addition of 69.0 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 solution is cooled to 05° in an ice bath and stirred.溶液在 0-5 下冰浴搅拌。The stopper is replaced by a dropping funnel, and a cold mixture 515° of108 g. 1.50 moles of freshly distilled 2-butanone and 482 g. 3.30 moles ofdiethyl oxalate Note 1 is added gradually 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。 After the addition is complete, the thick,orange-red mixture is allowed to warm with continued stirring to room temperature,heated under reflux for 30 minutes, and cooled again to 0in an ice ba°th.完全加入后，橘红色的粘稠物连续搅拌至室温，加热回流30 分钟后在冰浴中冷却至0 。 The mixture is decomposed by stirring with 165 ml. of sulfuric acid 1:1 by volume added inportions.将 165ml浓硫酸（体积比1:1 ）在搅拌加入，分解混合物。The sodium sulfate可编辑资料 - - - 欢迎下载精品名师归纳总结学习资料 名师精选 - - - - - - - - - -第 4 页，共 10 页 - - - - - - - - - -可编辑资料 - - - 欢迎下载精品名师归纳总结资料word 精心总结归纳 - - - - - - - - - - - -formed is filtered by suction and washed with ethanol 150200 ml. Note 2.硫酸钠抽滤后用乙醇（150 200 ml）洗涤。 The washings and filtrate are combined and concentrated by evaporation .合并滤液和洗涤液后蒸发浓缩。The yellowish brownproduct which accumulates by slow crystallization is collected by filtration, washedwith small quantities 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 140150 g.粗产品140-150g。 Further evaporative concentration of the mother liquor followed bycooling furnishes an additional 4050 g. of the keto ester,此外将母液用冷冻蒸发浓缩后又得到40-50g的酮酯。 bringing the total yield to 180200 g. 5359%产品总共 180-200g（产率 53-59%） Note 2. This crude material m.p. 120130 ° is used in the next step.粗品（熔点120 130 ）用于下一步中A pure sample can be obtained bycrystallization from ethyl acetate after treatment with Norit activated carbon, m.p.160 162 °. 纯品是经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 witha sealed stirrer, a dropping funnel, and a reflux condenser, is placed 80 g. 1.1 moles of dimethylformamide 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 is immersed in an ice bath, and the internal temperature is maintained at 1020°, while 169 g.1.1 moles of phosphorus 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。Anexothermicreaction occurs withthe formationofthe phosphorus oxychloride - 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 the mixture.重新再冰浴下加入 250ml 的二氯乙烯。 When the internal temperature has been lowered to 5, a solu°tionof 67 g. 1.0 mole of freshly distilled pyrrole in 250 ml. of ethylene dichloride is added through aclean dropping funnel to 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 the addition is complete, the ice bath is replaced with a heating mantle, andthe mixture is stirred at the reflux temperature for 15 minutes, during which time there is copious 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 cooled to 25 30°, and to it is added through the dropping funnel a solution of 750 g. 5.5 moles of sodium acetate trihydrate Note 3 in about of water, cautiously at first, then as rapidly as 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，开头要当心，然后要尽可能的快。The reaction mixture is again refluxed for 15minutes, vigorous stirring being maintained all the while Note 4.反应物在充分搅拌下重新回流15分钟。可编辑资料 - - - 欢迎下载精品名师归纳总结学习资料 名师精选 - - - - - - - - - -第 5 页，共 10 页 - - - - - - - - - -可编辑资料 - - - 欢迎下载精品名师归纳总结资料word 精心总结归纳 - - - - - - - - - - - -The cooled mixture is transferred to a 3-l. separatory funnel, and the ethylene dichloride layer is removed. 冷却的混合物转移到分液漏斗中，出去二氯乙烯层。The aqueous phase isextracted 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 combined and washed with three 100-ml. portions ofsaturated aqueous sodium carbonate solution, which is added cautiously at first to avoid too rapidevolution of carbon dioxide. 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，通入时要当心不要太快。The non- aqueous solution is then dried overanhydrous sodium carbonate, the solvents are distilled, and the remaining liquid is transferred to a Claisen flask and distilled from an oil bath under 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。The aldehyde boils at 78°at 2 mm.; there is very little fore-run and very little residue.醛沸点 78 度在 2mm。很少有预留 无和残渣。 The yield of crude 2-pyrrolealdehyde is 8590 g. 8995%, as an almost water-whiteliquid which soon crystallizes.当几乎透亮的液体会立刻结晶，粗品产量85-90g（ 89-95% ）。 A sample dried on a clay plate melts at 35 40°. 样品在素烧瓷板上干燥，熔点35-40 度。 The crude product is purified by dissolving in boiling petroleum ether b.p. 4060°, in the ratio of 1 g. of crude 2-pyrrolealdehyde to 25 ml. of solvent, and cooling the solution slowly to roomtemperature, 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 the crude in approximately 85% recovery.纯品醛是从粗品中得到，收 率 85%。 The over-all yield from pyrrole is 7879% of pure 2-pyrrolealdehyde, m.p. 44 45°. 总得率为 78-79% 熔点 44-45 度。（1）反应式可编辑资料 - - - 欢迎下载精品名师归纳总结学习资料 名师精选 - - - - - - - - - -第 6 页，共 10 页 - - - - - - - - - -可编辑资料 - - - 欢迎下载精品名师归纳总结资料word 精心总结归纳 - - - - - - - - - - - -4、(1) In a 3L. round-bottomed flask Note 1 fitted with a reflux condenser areplaced 625 cc. of 95 per cent alcohol Note 2, 500 cc. of water, 500 g. 476 cc., 4.7moles of pure benzaldehyde Note 3, and 50 g. of sodium cyanide 9698 percent.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 Note 4.混合物加热并保持沸腾1.5小时。 In the courseof about twenty minutes, crystals begin to separate from the hot solution.在 20 分钟后晶体开头从热溶液中析出。At the end of the thirty minutes, the solution is cooled,filtered with suction, and washed with a little water.在最终的30 分钟，冷却溶液，抽滤并用少量水洗涤The yield of dry crude benzoin, which is white or light yellow, is450 460 g.有 450-460g白色或亮黄色的干燥的安眠香。90 92 per cent of the theoretical amount.理论产率90-92%。In order to obtain it completely pure, thecrude substance is recrystallized from 95 per cent alcohol, 90 g. of crude material being dissolved in about 700 cc. of boiling alcohol; upon cooling, a yield of 83 g. ofwhite, pure benzoin which melts at 129is obta°ined.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700ml沸腾的酒精中，冷却，得到 83g熔点为129摄氏度的白色安眠香纯品。(2) Ina 1L.three-necked round-bottomedflaskequipped witha mechanical stirrer, short reflux condenser, and bent g