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1、精品文档，仅供学习与交流，如有侵权请联系网站删除1、About 216224 g. (1.621.68 moles) of powdered anhydrous aluminum chloride is added to a 1Lthree-necked flask.在1L的三口烧瓶中加入大约216-224g(1.621.68 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 dropping funnel
2、 in a slow stream over a period of 2030 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。Considerable heat is evolved, and, if the drops of ketone are 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, the mixture becomes a viscous bal
3、l-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 or more 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
4、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 acetophenone is complexed with aluminum chloride, ranges in color from tan to 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.,
5、 0.80 mole) is added dropwise to the well-stirred mixture over a 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 steam bath 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
6、mixture of 1.3 l. of cracked ice and 100 ml. of concentrated 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的烧杯中混合均匀。Part of the cold aqueous layer is added to the reaction flask to decompose whatever part of the reaction mixture remains there, and the resulting mixture is
7、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 the mixture 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 and 100 ml. of 5% aqueous sodium bicarbonate solution, dried
8、with anhydrous sodium sulfate, 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 grams of heavy dark residue by distillation at reduced pressur
9、e. 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。The colorless distillate is carefully fractionated to obtain 94100 g.通过分馏，得到无色的流出液94-100g2、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-seale
10、d 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 d
11、ropping funnel, and a cold mixture (515) of 108 g. (1.50 moles) of freshly distilled 2-butanone and 482 g. (3.30 moles) of diethyl 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,
12、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 0 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 mixture is decomposed by stirring with 165 ml. of sulfuric acid (1:1 by volume) added in
13、portions.将165ml浓硫酸（体积比1:1）在搅拌加入，分解混合物。 The sodium sulfate formed is filtered by suction and washed with ethanol (150200 ml.) (Note 2). 硫酸钠抽滤后用乙醇（150200 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 brown product which accumulates by slow cr
14、ystallization is collected by filtration, washed with 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 by cooling furnishes an additional 4050 g. of the k
15、eto 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120130）用于下一步中 A pure sample can be obtained by crystallization from ethyl acetate after treatment with Norit activated ca
16、rbon, m.p. 160162.纯品是经过活性炭处理后在乙酸乙酯中结晶得到，熔点160162。The procedure for 2- pyrrolealdehyde 2-吡咯甲醛In a 3-l. three-necked round-bottomed flask, fitted with a 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80
17、g（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 15 minutes. 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
18、occurs with the formation of the 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。W
19、hen the internal temperature has been lowered to 5, a solution of 67 g. (1.0 mole) of freshly distilled pyrrole in 250 ml. of ethylene dichloride is added through a clean 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
20、拌边滴加。After the addition is complete, the ice bath is replaced with a heating mantle, and the 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 2530, and to i
21、t 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，开始要小心，然后要尽可能地快。The reaction mixture is again refluxed for 15 minutes, vigorous
22、 stirring being maintained all the while (Note 4). 反应物在充分搅拌下重新回流15分钟。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 is extracted three times with a total of about 500 ml. of ether. 水相用500ml乙醚分三次萃取。
23、The ether and ethylene chloride solutions are combined and washed with three 100-ml. portions of saturated aqueous sodium carbonate solution, which is added cautiously at first to avoid too rapid evolution 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，通入时要小心不要太快。 The non- aqueous solution
24、 is then dried over anhydrous 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-ru
25、n 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-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 on a clay plate melts at 3540. 样品在素烧瓷板上干燥，熔点35-40度。The crude product is purified by dissol
26、ving 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 room 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 f
27、rom 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. 4445. 总得率为78-79%熔点44-45度。（1）反应式4、(1)In a 3L. round-bottomed flask (Note 1) fitted with a reflux condenser are placed 625 cc. of 95 per cent alcohol (Note 2), 500 cc.
28、 of water, 500 g. (476 cc., 4.7 moles) of pure benzaldehyde (Note 3), and 50 g. of sodium cyanide (9698 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 (Note 4). 混合物加热并保持沸腾1.5小时。In the course of about
29、 twenty minutes, crystals begin to separate from the hot solution. 在20分钟后晶体开始从热溶液中析出。At the end of the thirty minutes, the solution is cooled, filtered with suction, and washed with a little water. 在最后的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, is 450460 g.有45
30、0-460g白色或亮黄色的干燥的安息香。 (9092 per cent of the theoretical amount). 理论产率90-92%。In order to obtain it completely pure, the crude 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. of white, pure
31、 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700ml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-bottomed flask equipped with a mechanical stirrer, short reflux condenser, and bent glass tube reaching below the surface of the liquid for the introduction of
32、 hydrogen chloride, are placed 50 g. (0.36 mole) of p-nitrophenol (Note 1), 650 ml. of concentrated hydrochloric acid, 5 ml. of concentrated 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
33、二甲氧基甲烷。The mixture is stirred while the temperature is maintained at 70 2 for 45 hours by means of a water bath (Note 4). 在水浴中保持702度搅拌4-5小时。During this time hydrogen chloride is bubbled into the reaction mixture through the bent glass tube, and the excess gas is carried away through the reflux conde
34、nser 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气体吸收罩吸收。The 2- hydroxyl -5- nitrobenzyl chloride begins to separate as a solid about 1 hour after 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
35、whereby more crystals separate, after which the acid liquors are either filtered or decanted from the 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 by recrystallization 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 yi
36、eld is 46 g. (69% based on p-nitrophenol) of a white product melting at 129130.白色产物46g（对硝基苯酚含69%）熔点129-130度5、B.Benzyltrans-1,3-butadiene-1-carbamate. Adry, 1-l., three-necked, round-bottomed flask is equipped with a magnetic stirring bar, a thermometer, and a 250-ml., pressure-equalizing dropping fu
37、nnel bearing a nitrogen inlet. The flask is flushed withnitrogenand charged with49 g. (0.50 mole) oftrans-2,4-pentadienoic acid,80 g. (0.62 mole) ofN,N-diisopropylethylamine, and300 ml. ofacetone(Note 6). The resulting solution is stirred and cooled to 0 in anicesalt bath. A solution of55 g. (0.51 m
38、ole) ofethyl chloroformatein150 ml. ofacetoneis added over 30 minutes while the temperature is maintained below 0(Note 7). Stirring is continued for an additional 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 in
39、terval, keeping the temperature below 0. The contents of the flask are stirred for an additional 1015 minutes at 0(Note 9)and poured into a2-l. separatory funnelcontaining 500 ml. of ice-water. The acyl azide is isolated by extraction with six250-ml. portions oftoluene. The combinedtolueneextracts a
40、re dried overanhydrousmagnesium sulfatefor 20 minutes and concentrated to a volume ofca.300 ml. on a rotary evaporator at a water bath temperature of 4050(Note 10).Caution! The acyl azide is potentially explosive. The solution should not be evaporated to dryness.While thetoluenesolution is being con
41、centrated, adry, 2-l., three-necked, round-bottomed flask equipped with a mechanical stirrer, a 500-ml. pressure-equalizing dropping funnel, a simple distillation head, and a heating mantleis charged with43 g. (0.40 mole) ofbenzyl alcohol,250 mg. of4-tert-butylcatechol(Note 11), and200 ml. oftoluene
42、. About 30 ml. of toulene is distilled from the flask to remove trace amounts of water, and the distillation head is replaced with a condenser fitted with anitrogeninlet. Thetoluenesolution is stirred and heated at a rapid reflux under anitrogenatmosphere as thetoluenesolution of the acyl azide is a
43、dded over 30 minutes. The disappearance of the acyl azide and isocyanate is followed by IR analysis(Note 12). Conversion to the carbamate is complete in 1030 minutes, after which the solution is cooled rapidly to room temperature by immersing the flask in anice bath. Thetolueneis rapidly removed on
44、a rotary evaporator with the water bath at 4050, producing a yellow solid residue(Note 13)which is dissolved in50 ml. of 95%ethanoland allowed to crystallize in a freezer at 25 for several hours. Two crops of pale yellow crystals, m.p.6972, are isolated which total3946 g.after drying under reduced p
45、ressure. Concentration of the mother liquor affords an oily residue that is placed on a6 80-cm. column packed with 500 g. of silica gel(Note 14)and eluted with1:9 (v/v)ethyl acetatehexane. An additional1112 g.of crystalline product is obtained from the chromatography, raising the total yield to5058
46、g.(4957%) of nearly purebenzyltrans-1,3-butadiene-1-carbamate, a pale yellow solid, m.p.7073(Note 15).苄反- 1，3 -丁二烯-1 -氨基甲酸。一个干燥，1 L，配备磁性搅拌棒和温度计的250毫升三口圆底烧瓶，有压力平衡滴液漏斗轴承氮入口。烧瓶与氮冲洗后，秤取49克（0.50摩尔）的反式-2,4 - 氨基酸，80克（0.62摩尔）的N，N-二异丙基和300毫升的丙酮至烧瓶中。搅拌，在冰盐浴冷却至0。55克的溶液（0.51摩尔）氯甲酸乙酯150毫升，温度保持低于0 注入，丙酮加入要超过30分钟。
47、在0 下继续搅拌30分钟，得到后的冷冻液65克再加入170毫升的叠氮化钠 。加水超过20分钟的时间间隔，保持温度低于0 。烧瓶的内的反应物每隔10-15分钟，在0搅拌，成2 L 直至分液漏斗中含有500毫升。冰水。酰基叠氮分离提取至六个250毫升瓶中。结合甲苯提取20分钟，无水硫酸镁 干燥，集中到一个体积约300毫升 的水浴温度40-50 旋转蒸发器中。甲苯溶液浓缩，干燥至500毫升，加入2 L装有机械搅拌器的三口圆底烧瓶。压力平衡滴液漏斗，一个简单的蒸馏头，和一个加热地幔，得产品是43克（0.40摩尔）。苯甲醇250毫克， 4 -叔丁基 邻苯二酚200毫升 和甲苯约30毫升。搅拌并加热下快速
48、回流氮气氛下，甲苯酰基叠氮的解决方案是增加了超过30分钟。其次是红外线分析酰基叠氮化物和异氰酸酯的消失 。转换的氨基甲酸酯类是在10-30分钟完成，沉浸在烧瓶后，解决的办法是冰浴迅速冷却至室温。甲苯是迅速取出在40-50水浴旋转蒸发器上，产生一个黄色的固体残渣，50毫升 。用95的乙醇，并允许在-25 冷冻几个小时结晶 。得到的两种产物淡黄色晶体，熔点69-72 ，干燥后减压，孤立得总39-46克， 。母液提供了一个油性残留物，放置在6 80厘米，列挤满了500克的硅胶和1:9（V / V）的洗脱乙酸乙酯-正己烷。从色谱中得到额外的11-12克的结晶产品，总收率提高到50-58克（49-57），近纯苄反式-1,3 -丁二烯- 1 -氨基甲酸酯，黄色固体，熔点70-73 6、【精品文档】第 7 页