药物合成反应(闻韧_第三版)课后翻译
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1、216-224g(1.62–1.68 moles)的无水三氯化铝。
While the free-flowing catalyst isfunnel in a slow stream over a period of 20–30 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added, the mixture 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 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 thebrown.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。
《药物合成反应(闻韧主编第三版)》人名反应整理一、卤化反应1、Hunsdriecke反应(汉斯狄克反应):羧酸银盐和溴或碘反应,脱去二氧化碳,生成比原反应物少一个碳原子的卤代烃。
2、Sandmeyer反应(桑德迈尔反应):用氯化亚铜或溴化亚铜在相应的氢卤酸存在下,将芳香重氮盐转化成卤代芳烃。
3、Gattermann反应(加特曼反应):将Sandmeyer反应条件改为铜粉和氢卤酸。
4、Schiemann反应(席曼反应):将芳香重氮盐转化成不溶性的重氮氟硼酸盐或氟磷酸盐,或将芳胺直接用亚硝酸钠和氟硼酸进行重氮化,此重氦盐再经热分解(有时在氟化钠或铜盐存在下加热),就可以制得较好收率的氟代芳烃。
二、烃化反应5、Willamson合成(威廉姆森合成):醇在碱(钠,氢氧化钠,氢氧化钾等) 存在下与卤代烃反应生成醚的反应。
6、Gabriel合成(盖布瑞尔合成):将氨先制备成邻苯二甲酰亚胺,利用氮上氢的酸性,先与氢氧化钾形成钾盐,然后与卤代烃作用,得N-烃基邻苯二甲酰亚胺,肼解或酸水解即可得纯伯胺。
7、Delepine反应(德勒频反应):用卤代烃与环六亚甲基四胺(乌洛托品Methenamine)反应得季铵盐,然后水解可得伯胺。
8、Leuckart-Wallach反应(鲁卡特-瓦拉赫反应):用甲酸及其铵盐可以对醛酮进行还原烃化,得各类胺。
9、Ullmann反应(沃尔曼反应):卤代芳烃与芳香伯胺在铜或碘化铜及碳酸钾存在并加热的条件下可得二苯胺及其同系物。
三、酰化反应10、Friedel-Crafts反应(傅列德尔-克拉夫茨反应,也称傅-克酰基化反应):羧酸及羧酸衍生物在质子酸或Lewis酸的催化下,对芳烃进行亲电取代生成芳酮的反应。
11、Hoesch反应(赫施):腈类化合物与氯化氢在Lewis 酸催化剂ZnCl2的存在下与烃基或烷氧基取代的芳烃进行反应可生成相应的酮亚胺,再经水解则羟基或烷氧基取代的芳香酮。
12、Gattemann反应(伽特曼反应):将羟基或烷氧基取代的芳烃在AlCl3、ZnCl2催化下与氰化氢及氯化氢反应生成牙胺盐酸盐,再经水解生成相应芳香醛的反应。
1、About 216–224 g. (1.62–1.68 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(1.62–1.68 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 dropping funnel in a slow stream over a period of 20–30 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 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。
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-L solution of aqueous 50% sodium hydroxide(Note 1), mechanically stirred in a 2-L, three-necked flask, was added, at 25°C, 114.0 g (0.5 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℃机械搅拌。
To this vigorously stirred suspension was added a mixture 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 rinsing the flask with three 75-mL portions 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 mixture 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。
About 216–224 g. (1.62–1.68 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(1.62–1.68 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 dropping funnel in a slow stream over a period of 20–30 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 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。
有回流冷凝器的3L圆底烧瓶中参加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 forminutes, 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450-460g白色或亮黄色的枯燥的安息香。
(90–92 per cent of the theoretical amount). 理论产率90-92%。
In order to obtain it pletely pure, the crude substance iswhich 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。
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 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参加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。
1、About 216–224 g. (1.62–1.68 moles) of powdered anhydrous is added to a1Lthree-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 , 81 g. (0.67 mole) of is added from the dropping funnel in a slow stream over a period of 20–30 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 has been added, the mixture 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 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 is complexed with , 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。
(128 g., 0.80 mole) is added dropwise to the well-stirred mixture over a period of 40 minutes . 在40分钟内在搅拌下把溴缓慢滴加到混合物中。
After all the has been added, the molten mixture is stirred at 80–85° 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 1.3 l. of cracked ice and 100 ml. of concentrated in a 2-l. beaker .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 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 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 solution, dried with anhydrous , 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 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. 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 94–100 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 is prepared in a 2-l. three-necked, round-bottomed flask fitted with a mercury-sealed stirrer, a reflux condenser carrying a drying tube, and a stopper by the addition of 69.0 g. (3 moles) of to 950 ml. of absolute . 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0-5℃下冰浴搅拌。
The stopper is replaced by a dropping funnel, and a cold mixture (5–15°) of 108 g. (1.50 moles) of freshly distilled and 482 g. (3.30 moles) of 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 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 (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 formed is filtered by suction and washed with (150–200 ml.) . 硫酸钠抽滤后用乙醇(150–200 ml)洗涤。
Thewashings 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 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 evaporative concentration of the mother liquor followed by cooling furnishes an additional 40–50 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 180–200 g. (53–59%)产品总共180-200g(产率53-59%) . This crude material (m.p. 120–130°) is used in the next step.粗品(熔点120–130℃)用于下一步中A pure sample can be obtained by crystallization from after treatment with activated , 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 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80g(1.1mol)的二甲基甲酰胺。