藥物合成反應(yīng)與設(shè)計翻譯部分(優(yōu).選)

1、藥物合成反應(yīng)與設(shè)計翻譯部分 (第三版 聞韌主編) 第一章翻譯：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的三口燒瓶中加入大約216-224g(1.62 - 1.68 moles)的無水三氯化鋁。 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. 自由流動的催化劑邊攪拌邊用滴液漏斗緩慢滴加 81g 苯乙酰。 Considerable heat is evolved, and, if the drops of ketone are not dispersed, darkening or charring occurs. 放熱反應(yīng)，假如滴加的酮不能 被分散，就會變黑或是碳化。 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. 當(dāng)三分之一的乙酰苯被滴加，反 應(yīng)混合物變成一個很難攪拌的粘性的球狀團(tuán)塊。 Turning of the stirrer by hand or more rapid addition of ketone is necessary at this point. 在這時，改用手動攪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，當(dāng)反應(yīng)溫度超過 180 C時。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. 當(dāng)快滴加完時， 團(tuán)塊開始融化， 表明苯乙酰已經(jīng)和三氯化鋁混合

5、完全， 顏色也逐漸 從黃褐色變?yōu)樽厣?Bromine (128 g., 0.80 mole) is added dropwise to the well-stirred mixture over a period of 40 minutes (Note 4). 在40分鐘內(nèi)在攪拌下把溴緩慢滴加到混合物中。 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蒸氣浴下攪拌 1小時。The complex

6、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).反應(yīng)物加入到1.3L碎冰和100ml濃鹽酸的混合物中在2L的燒杯中混合均勻。 Part of the cold aqueous layer is added to the reaction flask to decompose whatever part of the reaction mixture remai

7、ns there, and the resulting mixture is added to the beaker.把部分的冰水層加入到燒瓶中洗滌殘留物，然后合并到燒杯中。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 從混合物中用 150ml 萃取出來。 The extracts are combined, washed consecutively with 100 ml. of water and 100 ml. of 5% aq

8、ueous 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% 的小蘇打洗滌， 用無水硫酸鈉干燥。 The ether is removed by distillation at atmospheric pressure, and crude 3-bromoacetophenone is stripped from a few grams of heavy

9、 dark residue by distillation at reduced pressure. 乙醚在常壓下蒸餾， 微量的溴苯乙酮通過減壓蒸餾的方法從大量深色殘渣中被分離出來。The colorless distillate iscarefully fractio nated to obta in 94 - 100 g.通過分餾，得到無色的流出液94-100g第一章在1L的三口燒瓶中加入大約216-224g(1.62 - 1.68 moles)的無水三氯化鋁。自由流動的催化劑邊攪拌邊用滴液漏斗緩慢滴加 81g 苯乙酰。 放熱反應(yīng)， 假如滴加的酮不能被分散， 就會變 黑或是碳化。 當(dāng)三分之

10、一的乙酰苯被滴加， 反應(yīng)混合物變成一個很難攪拌的粘性的球狀團(tuán)塊。 在這時，改用手動攪拌或快速滴加酮是非常必要的。然而，速度不能太快，當(dāng)反應(yīng)溫度超過180 C時。當(dāng)快滴加完時，團(tuán)塊開始融化，表明苯乙酰已經(jīng)和三氯化鋁混合完全，顏色也逐 漸從黃褐色變?yōu)樽厣?。?0分鐘內(nèi)在攪拌下把溴緩慢滴加到混合物中。溴滴加完后，熔融混合物在80-85 C蒸氣浴下攪拌1小時。反應(yīng)物加入到1.3L碎冰和100ml濃鹽酸的混合物中在2L的燒杯中混合均勻。把部分的冰水層加入到燒瓶中洗滌殘留物， 然后合并到燒杯中。 分四次把深色的油從混 合物中用 150ml 萃取出來。合并萃取液，用 100ml 水和 100ml 5%的小蘇

11、打洗滌，用無水硫 酸鈉干燥。 乙醚在常壓下蒸餾， 微量的溴苯乙酮通過減壓蒸餾的方法從大量深色殘渣中被分 離出來。通過分餾，得到無色的流出液 94-100g第二章課后翻譯Preparation of cyclopropane 1,1- dicarboxylic acid 環(huán)丙烷 1,1-二甲酸的制備(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 (0.5 mol)

12、 of triethylbenzylammonium chloride(TEBA三乙基芐基氯化銨)Note 2). 1L的50%氫氧化鈉加入到 2L的三口燒瓶中，加入 TEBA三乙基芐基氯 化銨 114.0g( 0.5mol)在 25 C機械攪拌。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?jǐn)嚢柚粱鞈覡?，一次性加入丙二酸二乙?0.

13、0g (0.5mol )和 1,2-二溴乙烷141.0個(0.75mol)的混合物。The reaction mixture was vigorously stirred for 2 hr (Note 3). 反應(yīng)混合 物強烈攪拌 2 小時。 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. 把燒瓶中的物質(zhì)轉(zhuǎn)移到4L的錐形瓶中，并用 75ml 清水洗滌燒瓶三次。 The mixture w

14、as magnetically stirred by dropwise addition of 1 L of concentrated hydrochloric acid. 混合物在磁力攪拌下緩慢滴加濃鹽酸。 The temperature of the flask was maintained between 15 and 25C during acidification. 在酸化過程中燒瓶內(nèi)的溫度保持在 15-25 C之間。The aqueous layer was poured into a 4-L separatory funnel and extracted three times

15、with 900 mL of ether.反應(yīng)物的水層在 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. 水層用氯化鈉飽和，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 carbon. 合并乙醚液，

16、用 濃鹽水洗滌， 干燥，用活性炭脫色。 Removal of the solvent by rotary evaporation gave 55.2 g of a semisolid residue. 用旋轉(zhuǎn)蒸發(fā)器出去溶劑得 55.2g 的半固體。 The residue was triturateed with 100 mL of benzene.殘渣用 100ml 苯磨碎。Filtration of this mixture gave 43.1- 47.9 g (66-73%) of 1 as white crystals, mp 137 - 140 C過濾的混合物為 43.1-47.9g

17、(66 - 73%)白色晶體 熔點 137 - 140 CPreparation of mesitaldehyde (2,4,6- trimethyl benzaldehyde) 2,4,6-三甲基苯甲醛的制備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 a dropping funnel. 72g(0.

18、60mol)的1,3,5-三甲基苯和無水的二氯甲烷放入配有冷凝回流、攪拌和滴液漏斗裝置的三口燒瓶中。 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. 在冰浴的條件下，在三分鐘內(nèi)滴加 190g(110ml , 1.0mol)的四氯化鈦。While the solution is stirred and cooled, 57.5 g. (0.5 mole) ofdichloromet

19、hyl methyl ether 2 is added dropwise over a 25-minute period. 之后再冰浴和攪拌 下，在 25分鐘內(nèi)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. 當(dāng)開始滴加氯 代醚，則反應(yīng)開始(有氯化氫放出) After the addition is complete, the mixture is stirred f

20、or 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，混合物在冰浴下攪拌 5分鐘，移開冰浴反應(yīng) 30分鐘，再在35C下反應(yīng)15分鐘。 The reaction mixture is poured into a separatory funnel containing about 0.5 kg. of crushedis shaken thoroughly.反應(yīng)混合物移入分液漏斗，并加0.5kg的碎冰，充分振搖。The organiclayer

21、is separated, and the aqueous solution is extracted with two 50- ml. portions of methylene chloride. 棄去有機層，水層再用 50ml 的二氯甲烷分兩次萃取。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 滌。 A crystal of hydroquinone is added to the methylene chloride solutio

22、n (Note 1) which is then dried over anhydrous sodium sulfate. 對二苯酚晶體加入到二氯甲烷溶液中，在加入無水硫酸 鈉干燥。 After evaporation of the solvent, the residue is distilled to give the crude product, b.p. 68 -74 (0.9 mm.).蒸去溶劑便得到粗品沸點68-74 C( 0.9mm) After redistillation there isobtained 60 - 66 g. (81 - 89%) of mesitaldeh

23、yde; b.p. 113 - 115(11 mm.), n20D 1.5538.重蒸餾得到 60-66g (81-89%)的 2,4,6-三甲基苯甲醛沸點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-sealed stirrer, a reflux condenser carrying a dryin

24、g tube, and a stopper by the addition of 69.0 g. (3 moles) of sodium to 950 ml. of absolute ethanol. 69.0g ( 3mol )鈉和 950ml 無水乙醇在配有干燥回流冷凝管和汞封攪拌器的 2L三口圓底燒瓶中制備乙醇鈉。The solution is cooled to 0 - 5 in an ice bath and stirred.溶液在 0-5C下冰浴攪拌。The stopper is replaced by a dropping funnel, and a cold mixture (

25、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下低溫混合，在 30分鐘內(nèi)逐步滴加到溶液中。 After the addition is complete, the thick, orange-red mixt

26、ure 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，橘紅色的粘稠物繼續(xù)攪拌至室溫，加熱回流 30 分鐘后在冰浴中冷卻至 0C。 The mixture is decomposed by stirring with 165 ml. of sulfuric acid (1:1 by volume) added in portions. 將 165ml 濃硫酸

27、(體積比 1:1 )在攪拌加入，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).硫酸鈉抽濾后用乙醇(150 - 200 ml)洗滌。The washings and filtrate are combined and concentrated by evaporation . 合并濾液和洗滌液后蒸發(fā)濃縮。 The yellowish brown product which accumulates by slow crystalli

28、zation is collected by filtration, washed with small quantities of ice-cold water, and dried in air. 過濾緩慢析出的棕黃色產(chǎn)品用小劑量的冰水洗滌后在空氣 中干燥。The crude product weighs 140 - 150 g.粗產(chǎn)品 140-150g。 Further evaporativeconcen trati on of the mother liquor followed by cooli ng furni shes an additi onal 40 50 g. of the

29、keto ester, 此外將母液用冷凍蒸發(fā)濃縮后又得到 40-50g 的酮酯。 bringing the total yield to 180 -200 g. (53 - 59%)產(chǎn)品總共 180-200g (產(chǎn)率 53-59%) (Note 2). This crude material (m.p. 120 -130 ) is used in the next step.粗品(熔點 120 - 130 C)用于下一步中A pure sample can beobtained by crystallization from ethyl acetate after treatment with

30、 Norit activated carbon, m.p.160 - 162。.純品是經(jīng)過活性炭處理后在乙酸乙酯中結(jié)晶得到，熔點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 reflux condenser, is placed 80 g. (1.1 moles) of dimethylformamide (Note 1). 在配有封

31、閉攪拌器、 滴液漏斗和冷凝回流裝置的三口圓底燒瓶中放入 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 dropping funnel over a period of 15 minutes. 燒瓶浸入冰浴中，內(nèi)部溫度保 持在10-20 C, 169g (1.1mol)的磷酰氯通

32、過滴液漏斗在15分鐘內(nèi)滴加。An exothermic reactio noccurs with the formation of the phosphorus oxychloride - dimethylformamide complex. 放熱反 應(yīng)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，在攪拌 15 分鐘。 The ice bath is replaced, and 250 ml. of ethylene dichloride is

33、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 through a clean dropping funnel to the stirred, cooled mixture over a period of 1 hour.當(dāng)內(nèi)部溫度降到 5度時，

34、把67g( 1.0mol)新蒸餾的吡咯加入 到 250 二氯乙烯中，通過滴液漏斗在 1 小時內(nèi)低溫下邊攪拌邊滴加。 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， 用加熱裝置取代冰浴， 攪拌回流 15 分

35、鐘， 直到有大量氯化氫產(chǎn)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.當(dāng)混合物降溫到 25-30 C后，通過滴液漏斗加入750g (5.5mol )的三水醋酸鈉溶液，開始要小心，然后要盡可能

36、地快。 The reaction mixture is again refluxed for 15 minutes, vigorous stirring being maintained all the while (Note 4). 反應(yīng)物在充分?jǐn)嚢柘轮匦禄?流 15 分鐘。 The cooled mixture is transferred to a 3-l. separatory funnel, and the ethylene dichloride layer is removed. 冷卻的混合物轉(zhuǎn)移到分液漏斗中， 出去二氯乙烯層。 The aqueous phase is extra

37、cted 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 carbonate solution, which is added cautiously at first to avoid too rapid evolution of carbon dioxide

38、. 合并乙醚和氯乙烯溶液， 用 100ml 飽和碳酸鈉溶液 分三次洗滌， 然后通入二氧化碳， 通入時要小心不要太快。 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 水溶液用無水碳酸鈉干燥，蒸餾溶

39、劑，余下的溶液移入克氏燒瓶在油浴中減壓蒸餾。Thealdehyde boils at 78 at 2 mm.; there is very little fore-run and very little residue. 醛沸點 78度 在 2mm ;很少有預(yù)留無和殘渣。 The yield of crude 2-pyrrolealdehyde is 85 - 90 g. (89 - 95%), as an almost water-white liquid which soon crystallizes. 當(dāng)幾乎透明的液體會馬上結(jié)晶， 粗品產(chǎn)量 85-90g (89-95%)。A sampl

40、e dried on a clay plate melts at 35 - 40 .樣品在素?zé)砂迳细稍铮?熔點 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 room temperature, followed by refrigeration f

41、or a few hours. 粗品溶解在沸騰的石油醚 中(沸點 40-60 度)，一克粗品 2-甲基吡啶加入 25ml 溶劑，在室溫下冷卻，這后再冷凍數(shù)小 時。 The pure aldehyde is obtained from the crude in approximately 85% recovery. 純品醛是從粗 品中得到，收率 85%。The over-all yield from pyrrole is 78 - 79% of pure 2-pyrrolealdehyde, m.p.44 - 45 .總得率為78-79%熔點44-45度。第三章(1 )、69.0g (3mol)

42、鈉和950ml無水乙醇在配有干燥回流冷凝管和汞封攪拌器的2L三口圓底燒瓶中制備乙醇鈉。溶液在0-5C下冰浴攪拌。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下低溫混合，在 30分鐘內(nèi)逐步滴加到溶 液中。完全加入后，橘紅色的粘稠物繼續(xù)攪拌至室溫，加熱回流 30分鐘后在冰浴中冷卻至0C。將165ml濃硫酸(體積比1:1)在攪拌加入，分解混合物。硫酸鈉抽濾后用乙醇(150-200 ml)洗滌。合并濾液和洗滌液后蒸發(fā)濃縮。過濾緩慢析出的棕黃色產(chǎn)品用小劑量的冰 水洗滌后在空氣中干燥。粗產(chǎn)品140-150g。此外將母液用冷凍蒸發(fā)濃縮后又

43、得到40-50g的酮酯。產(chǎn)品總共180-200g (產(chǎn)率53-59%) (Note 2).粗品(熔點120 - 130C)用于下一步中. 純品是經(jīng)過活性炭處理后在乙酸乙酯中結(jié)晶得到，熔點160 - 162C。( 2) The procedure for 2- pyrrolealdehyde 2- 吡咯甲醛在配有封閉攪拌器、滴液漏斗和冷凝回流裝置的三口圓底燒瓶中放入80g (1.1mol)的二甲基甲酰胺。燒瓶浸入冰浴中，內(nèi)部溫度保持在10-20 C, 169g (1.1mol)的磷酰氯通過滴液漏斗在 15 分鐘內(nèi)滴加。放熱反應(yīng)生成磷酰氯二甲基甲酰胺化合物。移去冰浴，在攪拌15分鐘。重新再冰浴下加

44、入 250ml的二氯乙烯。當(dāng)內(nèi)部溫度降到 5度時，把67g (1.0mol )新蒸餾的 吡咯加入到 250 二氯乙烯中, 通過滴液漏斗在 1 小時內(nèi)低溫下邊攪拌邊滴加。 滴加完后, 用 加熱裝置取代冰浴,攪拌回流 15分鐘, 直到有大量氯化氫產(chǎn)生。當(dāng)混合物降溫到 25-30C后，通過滴液漏斗加入750g ( 5.5mol)的三水醋酸鈉溶液，開始要小心,然后要盡可能地快。反應(yīng)物在充分?jǐn)嚢柘轮匦禄亓?15分鐘。冷卻的混合物轉(zhuǎn)移到分液漏斗中, 出去二氯乙烯層。 水相用 500ml 乙醚分三次萃取。 合并乙 醚和氯乙烯溶液, 用 100ml 飽和碳酸鈉溶液分三次洗滌, 然后通入二氧化碳, 通入時要小心

45、 不要太快。 非水溶液用無水碳酸鈉干燥, 蒸餾溶劑, 余下的溶液移入克氏燒瓶在油浴中減壓 蒸餾。醛沸點78度在2mm ;很少有預(yù)留無和殘渣。當(dāng)幾乎透明的液體會馬上結(jié)晶，粗品產(chǎn) 量 85-90g(89-95%)。 .樣品在素?zé)砂迳细稍?熔點 35-40 度。粗品溶解在沸騰的石油醚中(沸點 40-60 度),一克粗品 2-甲基吡啶加入 25ml 溶劑,在室溫下冷卻, 這后再冷凍數(shù)小時。 純品醛是從粗品中得到,收率85%?？偟寐蕿?78-79%熔點 44-45度。第四章翻譯In a 3-l. round-bottomed flask (Note 1) fitted with a reflux co

46、ndenser 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 per cent).在配有回流冷凝器的3L圓底燒瓶中加入 625ml的 95%酒精、500ml 水、500g( 476ml, 4,7mol)的苯甲醛和 50g 96-98%的氰化鈉。The mixture is then heated and kept

47、 boiling for one-half hour (Note 4). 混合物加熱并保持沸騰 1.5小時。 In the course of about twenty minutes, crystals begin to separate from the hot solution. 在20分鐘 后晶體開始從熱溶液中析出。 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 分鐘， 冷卻溶液， 抽濾并用少

48、量水洗 滌 The yield of dry crude benzoin, which is white or light yellow, is 450- 460 g.有 450-460g 白色或亮黃色的干燥的安息香。(90 - 92 per cent of the theoretical amount). 理論產(chǎn)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

49、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.為了得到純度高的產(chǎn)品,粗產(chǎn)品要在酒精中重結(jié)晶, 90g 粗品溶解在 700ml 沸騰的酒精中,冷卻, 得到 83g 熔 點為 129攝氏度的白色安息香純品。In a 1-l. three-necked round-bottomed flask equipped with a mechanical stirrer, short refl

50、ux 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 1), 650 ml. ofconcentrated hydrochloric acid, 5 ml. of concentrated sulfuric acid （Note 2）, and 76 g. （1 mole） of methylal （Note 3

51、）. 在配有機械攪拌， 短期冷凝回流器和一個為的是深入液面下通氯化氫氣體 的彎曲的玻璃管三口圓底燒瓶中加入50g（0.36mol ）對硝基苯酚， 650ml 的濃鹽酸， 5ml 的濃硫酸和 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 by means of a water bath （Note 4）. 在水浴中保持 70 2 度攪拌 4-5 小時。 During this time hydrogen chloride is bubbl

52、ed 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 trap （Note 5）. 在此期間通過玻璃彎管把氯化氫氣體通入反應(yīng)混合物 中，過量的氣體被帶到回流冷凝器被氣體吸收罩吸收。The 2- hydroxyl -5- nitrobenzylchloride begins to separate as a solid about 1 hour aft

53、er the beginning of the reaction. 在反應(yīng)開 始后的一個小時， 2-羥基-5-硝基苯氯化物作為固體被分離。At the end the mixture is cooled inice 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卻 1 小時，使更多的晶體析出， 之后把酸性液體過濾或傾析得到晶體。 The 2-hydroxy-5

54、-nitrobenzyl chloride is purified by recrystallization from 125 ml. of hot benzene 2- 羥基-5-硝基苯氯化物在熱的苯中重結(jié)晶純化。（Note 7）. The yield is 46 g. （69% based on p-ni trophe nol） of a white product melti ng at 129-130 .白色產(chǎn)物46g （對硝基苯酚含 69%）熔點129-130度第四章（1 ）、在配有回流冷凝器的3L圓底燒瓶中加入 625ml的95%酒精、500ml水、500g （476ml，4,7m

55、ol）的苯甲醛和50g 96-98%的氰化鈉?；旌衔锛訜岵⒈３址序v1.5小時。在20分鐘后晶體開始從熱溶液中析出。在最后的 30分鐘，冷卻溶液，抽濾并用少量水洗滌有 450-460g 白色或亮黃色的干燥的安息香。理論產(chǎn)率90-92%。為了得到純度高的產(chǎn)品，粗產(chǎn)品要在酒精中重結(jié)晶，90g粗品溶解在700ml沸騰的酒精中，冷卻，得到83g熔點為129攝氏度的白色安息香純品。（2）、在配有機械攪拌，短期冷凝回流器和一個為的是深入液面下通氯化氫氣體的彎曲的玻璃管三口圓底燒瓶中加入50g （0.36mol）對硝基苯酚，650ml的濃鹽酸，5ml的濃硫酸和76g（1mol）的二甲氧基甲烷。在水浴中保持 7

56、0 2度攪拌4-5小時。在此期間通過玻璃彎管把 氯化氫氣體通入反應(yīng)混合物中， 過量的氣體被帶到回流冷凝器被氣體吸收罩吸收。 在反應(yīng)開 始后的一個小時， 2-羥基-5-硝基苯氯化物作為固體被分離。最后把混合物在冰中冷卻 1 小時，使更多的晶體析出， 之后把酸性液體過濾或傾析得到晶體。2-羥基-5-硝基苯氯化物在熱的苯中重結(jié)晶純化。白色產(chǎn)物46g （對硝基苯酚含69%）熔點129-130度第五章翻譯芐反 - 1 ， 3 - 丁二烯 -1 - 氨基甲酸。一個干燥，1 - L,配備磁性攪拌棒，溫度計，和一個250毫升三口圓底燒瓶，壓力平衡滴液漏斗軸承氮入口。燒瓶與氮沖洗和收取 49 克。（0.50 摩爾）的反式 -2,4 - pentadienoic 酸， 80 克。 （0.62摩爾） 的 N ， N -二異丙基，和 300毫升。丙酮 （注 6） 。最終的解決方案 是攪拌和在冰鹽浴冷卻至0C 。55克的溶液 （0.51摩爾）氯甲酸乙酯在150毫升。而溫度保持低于 0 （注 7），丙酮加入超過 30 分鐘。攪拌繼續(xù)在 0 為一個額外的 30 分鐘， 之后的冷凍液 65克（1.0 痣） 在 170毫升的疊氮化鈉（注 8） 。加水超過 20 分鐘的時間 間隔，保持溫度低于 0 。燒瓶的內(nèi)容是一個額外的 10-15 分鐘，在 0 （注 9）攪拌， 澆成 2 -