药物合成反应与设计翻译部分(优.选)

1、药物合成反应与设计翻译部分 (第三版 闻韧主编) 第一章翻译：About 216 - 224 g. (1.62 - 1.68 moles) of powdered an hydrous alumi num chloride is added to a ILthree-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。 While the free-flowing catalyst is stirred (Note 3), 81 g. (0.67 mole) of acetophenone is added from the

2、 dropp ing funnel in a slow stream over a period of 20 30 minu tes. 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 mixtu

3、re 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 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

4、above 180 .然而，速度不能太快，当反应温度超过 180 C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

5、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 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 80- 85 ° on a steam bath for 1hour.溴滴加完后，熔融混合物在80-85C蒸气浴下搅拌 1小时。The c

6、omplex is added inportions to a well-stirred 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 mixtur

7、e remains there, 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 thatsettles 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. o

8、f 5% aqueous sodium bicarbonate solution, dried 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 o

9、f 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离出来。The colorless distillate iscarefully fractio nated to obta in 94 - 100 g.通过分馏，得到无色的流出液94-100g第一章在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。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。 放热反应， 假如滴加的酮不能被分散， 就会变 黑或是碳

10、化。 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。 在这时，改用手动搅拌或快速滴加酮是非常必要的。然而，速度不能太快，当反应温度超过180 C时。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。在40分钟内在搅拌下把溴缓慢滴加到混合物中。溴滴加完后，熔融混合物在80-85 C蒸气浴下搅拌1小时。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。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。 分四次把深色的油从混 合物中用 150ml 萃取出来。合并萃取液，用 100ml 水和 100m

11、l 5%的小苏打洗涤，用无水硫 酸钠干燥。 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。通过分馏，得到无色的流出液 94-100g第二章课后翻译Preparation of cyclopropane 1,1- dicarboxylic acid 环丙烷 1,1-二甲酸的制备(1). To a 1-Lsolution of aqueous 50% sodium hydroxide (Note 1), mechanically stirred in a 2-L, three-necked flask, was added, at 25 C, 114.0g (0

12、.5 mol) of triethylbenzylammonium chloride(TEBA三乙基苄基氯化铵)Note 2). 1L的50%氢氧化钠加入到 2L的三口烧瓶中，加入 TEBA三乙基苄基氯 化铵 114.0g( 0.5mol)在 25 C机械搅拌。To this vigorously stirred suspension was added amixture of 80.0 g (0.5 mol) of diethyl malonate and 141.0 g (0.75 mol) of 1,2-dibromoethane all at once.充分搅拌至混悬状，一次性加入丙二

13、酸二乙酯80.0g (0.5mol )和 1,2-二溴乙烷141.0个(0.75mol)的混合物。The reaction mixture was vigorously stirred for 2 hr (Note 3). 反应混合 物强烈搅拌 2 小时。 The contents of the flask were transferred to a 4-L Erlenmeyer flask by rin si ng the flask with three 75-mL portio ns of water. 把烧瓶中的物质转移到4L的锥形瓶中，并用 75ml 清水洗涤烧瓶三次。 The mi

14、xture was magnetically stirred by dropwise addition of 1 L of concentrated hydrochloric acid. 混合物在磁力搅拌下缓慢滴加浓盐酸。 The temperature of the flask was maintained between 15 and 25°C during acidification. 在酸化过程中烧瓶内的温度保持在 15-25 C之间。The aqueous layer was poured into a 4-L separatory funnel and extracted

15、 three times with 900 mL of ether.反应物的水层在 4L的分液漏斗中用 900ml乙醚分三次萃取。 The aqueous layer was saturated with sodium chloride and extracted three times with 500 mL of ether. 水层用氯化钠饱和，并且用 500ml 乙醚分三次萃取。 The ether layers were combined, washed with 1 L of brine, dried (MgSO4), and decolorized with activated c

16、arbon. 合并乙醚液，用 浓盐水洗涤， 干燥，用活性炭脱色。 Removal of the solvent by rotary evaporation gave 55.2 g of a semisolid residue. 用旋转蒸发器出去溶剂得 55.2g 的半固体。 The residue was triturateed with 100 mL of benzene.残渣用 100ml 苯磨碎。Filtration of this mixture gave 43.1- 47.9 g (66-73%) of 1 as white crystals, mp 137 - 140 °

17、 C过滤的混合物为 43.1-47.9g(66 - 73%)白色晶体 熔点 137 - 140° CPreparation of mesitaldehyde (2,4,6- trimethyl benzaldehyde) 2,4,6-三甲基苯甲醛的制备Asolution of 72 g. (0.60 mole) of mesitylene in 375 ml. of dry methylene chloride is placed in a 1-l. three-necked flask equipped with a reflux condenser, a stirrer, and

18、 a dropping funnel. 72g(0.60mol)的1,3,5-三甲基苯和无水的二氯甲烷放入配有冷凝回流、搅拌和滴液漏斗装置的三口烧瓶中。 The solution is cooled in an ice bath, and 190 g. (110 ml., 1.0 mole) of titanium tetrachloride is added over a period of 3 minutes. 在冰浴的条件下，在三分钟内滴加 190g(110ml , 1.0mol)的四氯化钛。While the solution is stirred and cooled, 57.5 g

19、. (0.5 mole) ofdichloromethyl methyl ether 2 is added dropwise over a 25-minute period. 之后再冰浴和搅拌 下，在 25分钟内滴加 57.5g (0.5mol)滴加二氯甲基甲醚。The reaction begins (as indicatedby evolution of hydrogen chloride) when the first drop of chloro ether is added. 当开始滴加氯 代醚，则反应开始(有氯化氢放出) After the addition is complete

20、, the mixture is stirred for 5 minutes in the ice bath, for 30 minutes without cooling, and for 15 minutes at 35° . 在滴加完成ice and后，混合物在冰浴下搅拌 5分钟，移开冰浴反应 30分钟，再在35C下反应15分钟。 The reaction mixture is poured into a separatory funnel containing about 0.5 kg. of crushedis shaken thoroughly.反应混合物移入分液漏斗，并

21、加0.5kg的碎冰，充分振摇。The organiclayer is separated, and the aqueous solution is extracted with two 50- ml. portions of methylene chloride. 弃去有机层，水层再用 50ml 的二氯甲烷分两次萃取。The combined organicsolution is washed three times with 75-ml. portions of water. 合并萃取液，用 75ml 水分三次洗 涤。 A crystal of hydroquinone is added t

22、o the methylene chloride solution (Note 1) which is then dried over anhydrous sodium sulfate. 对二苯酚晶体加入到二氯甲烷溶液中，在加入无水硫酸 钠干燥。 After evaporation of the solvent, the residue is distilled to give the crude product, b.p. 68 -74 ° (0.9 mm.).蒸去溶剂便得到粗品沸点68-74 °C( 0.9mm) After redistillation there i

23、sobtained 60 - 66 g. (81 - 89%) of mesitaldehyde; b.p. 113 - 115°(11 mm.), n20D 1.5538.重蒸馏得到 60-66g (81-89%)的 2,4,6-三甲基苯甲醛沸点113-115C(11mm)。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-

24、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 0 - 5° in an ice bath and stirred.溶液在 0-5C下冰浴搅拌。The stopp

25、er is replaced by a dropping funnel, and a cold mixture (5-15° ) 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 C下低温混合，在 30分钟内逐步滴加到

26、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 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 0C。 The mixture is decomposed by stirring with 16

27、5 ml. of sulfuric acid (1:1 by volume) 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 suct ion and washed with etha no I (150- 200 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

28、蒸发浓缩。 The yellowish brown product which accumulates 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 140 - 150 g.粗产品 140-150g。 Further evaporativeconcen trati on of the mother

29、liquor followed by cooli ng furni shes an additi onal 40 50 g. of theketo 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 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 C)用于下一步中A pure samp

30、le can beobtained by crystallization 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 - 162C。 Theprocedure 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 reflu

31、x 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 internaltemperature is maintained at 10- 20° , while 169 g. (1.1 moles) of phosphorus oxychloride isadded through the droppi

32、ng funnel over a period of 15 minutes. 烧瓶浸入冰浴中，内部温度保 持在10-20 °C, 169g (1.1mol)的磷酰氯通过滴液漏斗在15分钟内滴加。An exothermic reactio noccurs 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 (N

33、ote 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 solution of 67 g. (1.0 mole) of freshly distilled pyrrole in 250 ml. of ethylene dichloride is added thro

34、ugh 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

35、, 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, cautious

36、ly at first, then as rapidly as possible.当混合物降温到 25-30 C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 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 funn

37、el, 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。 The ether and ethylene chloride solutions are combined and washed with three 100-ml. portions of saturated aqueous sodium

38、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 is then dried over anhydrous sodium carbonate, the solvents are distilled, and the remaining liquid is transferred

39、 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。Thealdehyde 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 85 - 90 g. (89 -

40、 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 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

41、-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 from the crude in approximately 85% recovery. 纯品醛是从粗 品中得到，收率 85%。The

42、over-all yield from pyrrole is 78 - 79% of pure 2-pyrrolealdehyde, m.p.44 - 45° .总得率为78-79%熔点44-45度。第三章(1 )、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。溶液在0-5C下冰浴搅拌。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 5-15C下低温混合，在 30分钟内逐步滴加到溶 液中。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

43、C。将165ml浓硫酸(体积比1:1)在搅拌加入，分解混合物。硫酸钠抽滤后用乙醇(150-200 ml)洗涤。合并滤液和洗涤液后蒸发浓缩。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。粗产品140-150g。此外将母液用冷冻蒸发浓缩后又得到40-50g的酮酯。产品总共180-200g (产率53-59%) (Note 2).粗品(熔点120 - 130C)用于下一步中. 纯品是经过活性炭处理后在乙酸乙酯中结晶得到，熔点160 - 162C。( 2) The procedure for 2- pyrrolealdehyde 2- 吡咯甲醛在配有封闭搅拌器、滴液漏斗和冷凝回流装置的三

44、口圆底烧瓶中放入80g (1.1mol)的二甲基甲酰胺。烧瓶浸入冰浴中，内部温度保持在10-20 C, 169g (1.1mol)的磷酰氯通过滴液漏斗在 15 分钟内滴加。放热反应生成磷酰氯二甲基甲酰胺化合物。移去冰浴，在搅拌15分钟。重新再冰浴下加入 250ml的二氯乙烯。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。 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。当混合物降温到 25-30C后，通过滴液漏斗加入750g ( 5.5mol)的三水醋酸钠溶液，开始要小

45、心,然后要尽可能地快。反应物在充分搅拌下重新回流 15分钟。冷却的混合物转移到分液漏斗中, 出去二氯乙烯层。 水相用 500ml 乙醚分三次萃取。 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。 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。醛沸点78度在2mm ;很少有预留无和残渣。当几乎透明的液体会马上结晶，粗品产 量 85-90g(89-95%)。 .样品在素烧瓷板上干燥,熔点 35-40 度。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

46、,在室温下冷却, 这后再冷冻数小时。 纯品醛是从粗品中得到,收率85%。总得率为 78-79%熔点 44-45度。第四章翻译In a 3-l. round-bottomed flask (Note 1) fitted with a reflux condenser are placed 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 (96 - 98 p

47、er 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 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

48、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 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). 理论产率 90-92%。In order

49、 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 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 700

50、ml 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。In a 1-l. 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 hydrogen chloride, are placed 50 g. (0.36 mole) of p-nitrophenol (Note

51、 1), 650 ml. ofconcentrated 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 ）的二甲氧基甲烷。 The mixture is stirred while the temperature is mainta

52、ined at 70± 2° for 4 - 5 hours 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 mixture through the bent glass tube, and the excess gas is carried away through the reflux condenser to a hood or gas- absorption

53、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- nitrobenzylchloride 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 inice for 1 hour whereby more crystals separate,

54、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 yield is 46 g. （69% based on

55、p-ni trophe nol） of a white product melti ng at 129-130 ° .白色产物46g （对硝基苯酚含 69%）熔点129-130度第四章（1 ）、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。混合物加热并保持沸腾1.5小时。在20分钟后晶体开始从热溶液中析出。在最后的 30分钟，冷却溶液，抽滤并用少量水洗涤有 450-460g 白色或亮黄色的干燥的安息香。理论产率90-92%。为了得到纯度高的产品，粗产品要在酒精中重结晶，90g粗

56、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）、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。在水浴中保持 70± 2度搅拌4-5小时。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。 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。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

57、晶体。2-羟基-5-硝基苯氯化物在热的苯中重结晶纯化。白色产物46g （对硝基苯酚含69%）熔点129-130度第五章翻译苄反 - 1 ， 3 - 丁二烯 -1 - 氨基甲酸。一个干燥，1 - L,配备磁性搅拌棒，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 0C 。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 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