1、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 in a slow stream ove
2、r 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 ball-like mass that is
3、 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，当反应温度超过180时。 Near the end
4、 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., 0.80 mole) is add
5、ed 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 mixture of 1.
6、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 added to
7、 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 with a
8、nhydrous 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 pressure.
9、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-sealed
10、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
11、 a dropping 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 c
12、omplete, 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
13、) added in 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（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 brown product which accumul
14、ates by slow crystallization 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
15、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 120130）用于下一步中 A pure sample can be obtained by crystallization from ethyl acetate after treatment w
16、ith Norit activated carbon, 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、
17、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 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
18、内滴加。An exothermic reaction 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 m
19、ixture. 重新再冰浴下加入250ml的二氯乙烯。When 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
20、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, 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
21、then cooled to 2530, 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，开始要小心，然后要尽可能地快。The reaction mixture is again re
22、fluxed for 15 minutes, 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。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
23、 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 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
24、时要小心不要太快。 The non- aqueous solution 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
25、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 85 90 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
26、 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 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
27、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. 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 place
28、d 625 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 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-
29、half hour (Note 4). 混合物加热并保持沸腾 1.5 小时。In the course of about 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 d
30、ry crude benzoin, which is white or light yellow, is 450460 g.有 450-460g 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 c
31、c. of boiling alcohol; 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 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
32、glass tube reaching below the surface of the liquid for the introduction of 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
33、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 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
34、bent glass tube, and the excess gas is carried away through the reflux condenser 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
35、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 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 recrystal
36、lization 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 product melting at 129130.白色产物 46g（对硝基苯酚含 69%）熔点 129-130 度5、B. Benzyl trans-1,3-butadiene-1-carbamate.A dry, 1-l., three-necked, round-bottomed flask is equipped with a
37、magnetic stirring bar, a thermometer, and a 250-ml., pressure-equalizing dropping funnel bearing a nitrogen inlet. The flask is flushed with nitrogen and charged with 49 g. (0.50 mole) of trans-2,4-pentadienoic acid, 80 g. (0.62 mole) of N,N-diisopropylethylamine, and 300 ml. of acetone (Note 6). Th
38、e resulting solution is stirred and cooled to 0 in an icesalt bath. A solution of 55 g. (0.51 mole) of ethyl chloroformate in 150 ml. of acetone is 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 chill
39、ed solution of 65 g. (1.0 mole) of sodium azide (Note 8) in 170 ml. of water is added over a 20-minute interval, keeping the temperature below 0. The contents of the flask are stirred for an additional 1015 minutes at 0 (Note 9) and poured into a 2-l. separatory funnelcontaining 500 ml. of ice-water
40、. The acyl azide is isolated by extraction with six 250-ml. portions of toluene. The combined tolueneextracts are dried over anhydrous magnesium sulfate for 20 minutes and concentrated to a volume of ca. 300 ml. on a rotary evaporator at a water bath temperature of 4050 (Note 10). Caution! The acyl
41、azide is potentially explosive. The solution should not be evaporated to dryness. While the toluene solution is being concentrated, a dry, 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 hea
42、ting mantle is charged with 43 g. (0.40 mole) ofbenzyl alcohol, 250 mg. of 4-tert-butylcatechol (Note 11), and 200 ml. of toluene. 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 a nitrogen inlet
43、. The toluene solution is stirred and heated at a rapid reflux under a nitrogen atmosphere as the toluene solution of the acyl azide is added 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 minu
44、tes, after which the solution is cooled rapidly to room temperature by immersing the flask in an ice bath. The toluene is rapidly removed on a rotary evaporator with the water bath at 4050, producing a yellow solid residue (Note 13) which is dissolved in 50 ml. of 95% ethanol and allowed to crystall
45、ize in a freezer at 25 for several hours. Two crops of pale yellow crystals, m.p. 6972, are isolated which total 3946 g. after drying under reduced pressure. Concentration of the mother liquor affords an oily residue that is placed on a 6 80-cm. column packed with 500 g. of silica gel (Note 14) and
46、eluted with 1:9 (v/v) ethyl acetatehexane. An additional 1112 g. of crystalline product is obtained from the chromatography, raising the total yield to 5058 g. (4957%) of nearly pure benzyl trans-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 -
47、L，配备磁性搅拌棒，温度计，和一个 250 毫升三口圆底烧瓶，压力平衡滴液漏斗轴承氮入口。烧瓶与氮冲洗和收取 49 克。（0.50 摩尔）的 反式 -2,4 - pentadienoic 酸，80 克。（ 0.62 摩尔） 的 N ， N -二异丙基，和 300 毫升。丙酮 （注6） 。最终的解决方案是搅拌和在冰盐浴冷却至 0 。55 克的溶液 （0.51 摩尔）氯甲酸乙酯在 150 毫升。而温度保持低于 0 （注 7），丙酮加入超过 30 分钟。搅拌继续在 0 为一个额外的 30 分钟，之后的冷冻液 65 克（1.0 痣） 在 170 毫升的叠氮化 钠（注 8） 。加水超过 20 分钟的时间
48、间隔，保持温度低于 0 。烧瓶的内容是一个额外的 10-15 分钟，在 0 （注 9）搅拌，浇成 2 - L 。分液漏斗中含有 500 毫升。冰水。酰基叠氮分离提取六个 250毫升。部分甲苯。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 。在水浴温度在 40-50 旋转蒸发器 （注 10） 。 注意！酰基叠氮是潜在的爆炸性。该解决方案不应该被蒸发干燥 的甲苯溶液浓缩， 干燥，2 - L，三口圆底烧瓶装有机械搅拌器，500 毫升。压力平衡滴液漏斗，一个简单的蒸馏头，和一个加热地幔的收费是 43 克 （0.40 摩尔），苯甲醇，250 毫克 。 4 - 叔 丁基
49、邻苯二酚（注 11），和 200 毫升 。甲苯。约 30 毫升。toulene 是从烧瓶蒸馏去除微量的水，蒸馏头是装有与冷凝器更换氮气入口。的甲苯溶液搅拌并加热下快速回流氮气氛下， 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 （注 12） 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，解决的办法是迅速冷却至室温冰浴。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（注 13）这是在解散 50 毫升 。95的乙醇，并允许在一个冷冻在-25 几个小时结晶 。两种作物的淡黄色晶体，熔点 69-72 ，孤立的总 39-46 克，干燥后减压 。母液浓度提供了一个油性残留物，放置在 6 80 厘米。列挤满了 500 克。硅
