下载文档原格式
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。
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。
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。
#2.11打卡# 完成学习目标第三章酰化反应Acylation Reaction1 定义：有机物分子中O、N、C原子上导入酰基的反应.2 分类：根据接受酰基原子的不同可分为：氧酰化、氮酰化、碳酰化3 用途：药物本身有酰基活性化合物的必要官能团结构修饰和前体药物羟基、胺基等基团的保护。
酰化机理：加成-消除机理加成阶段反应是否易于进行决定于羰基的活性：若L的电子效应是吸电子的，不仅有利于亲核试剂的进攻，而且使中间体稳定；若是给电子的作用相反。
根据上述的反应机理可以看出，作为被酰化物质来讲，无疑其亲核性越强越容易被酰化。
具有不同结构的被酰化物的亲核能力一般规律为；RCH2－＞R—NH－＞R—O－＞R—NH2＞R—OH。
在消除阶段反应是否易于进行主要取决于L的离去倾向：L-碱性越强，越不容易离去，Cl- 是很弱的碱，-OCOR的碱性较强些，OH-、OR-是相当强的碱，NH2-是更强的碱。
RCOCl＞(RCO)2O＞RCOOH 、RCOOR′ ＞RCONH2＞RCONR2′R: R为吸电子基团利于进行反应；R为给电子基团不利于反应R的体积若庞大，则亲核试剂对羰基的进攻有位阻，不利于反应进行酸碱催化碱催化作用是可以使较弱的亲核试剂H-Nu转化成亲核性较强的亲核试剂Nu-，从而加速反应。
酸催化的作用是它可以使羰基质子化，转化成羰基碳上带有更大正电性、更容易受亲核试剂进攻的基团，从而加速反应进行。
氧原子的酰化反应是一类形成羧酸酯的反应，是羧酸和醇的酯化反应，是羧酸衍生物的醇解反应醇的结构对酰化反应的影响伯醇(苄醇、烯丙醇除外）＞仲醇＞叔醇1) 羧酸为酰化剂：提高收率：(1)增加反应物浓度(2)不断蒸出反应产物之一(3)共沸除水、添加脱水剂或分子筛除水。
（无水CuSO4，无水Al2(SO4)3，(CF3CO)2O，DCC。
）加快反应速率:(1)提高温度(2)催化剂(降低活化能)催化剂(1)质子酸催化法: 无机酸：浓硫酸,氯化氢气体,有机酸：苯磺酸，对甲苯磺酸等。
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。
1、216-224g(1.62–1.68 moles)的无水三氯化铝。
While the free-flowing catalyst is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。
Near the end of the addition, the mass becomes molten and can be stirred easilygrams 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 sodium ethoxide is prepared in a 2-l. three-necked, round-bottomed flask fitted with amercury-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。
1、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。
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。
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 eitherranges 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 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。
四次把深色的油从混合物中用 150ml 萃取岀来。
The extracts are combined, washedto produce a temperature above 180° .然而，速度不能太快，当反应温度超过either heated or cooled. The molte n mass, in which the acet ophenon e is complexed with aluminum chloride, ranges in color from tan to brown.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。
混合均匀。
Part of the cold aqueous layer is added to the reacti on flask to deco mposewhatever part of the reactionmixture remains there, and the resultingmixture is addedto 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。
that settles out is extracted from the mixture with four 150-ml. p orti ons of etherAbout 216 — 224 g. — moles) of po wdered an hydrous aluminum chloride is added to a1Lthree-necked flask.在1L 的三口烧瓶中加入大约 216-224g - moles)的无水三氯化铝。
While the freeflow ing catalyst is stirred (Note 3), 81 g. mole) of acet ophenone is added from the dropping funnel in a slow stream over a p eriod 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。
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 amercury-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0-5℃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 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, 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 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 (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%）(Note 2). 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 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160–162℃。
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。
The flask is immersed in an ice bath, and the internal temperature is maintained at 10–20°, 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 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。
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 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. 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 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。
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 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。
