藥物合成反應課后翻譯

1、 .DOC資料. 1、About 216224 g. (1.621.68 moles) of powdered anhydrous HYPERLINK /orgsyn/chemname.asp?nameID=33169 t _top aluminum chloride is added to a 1Lthree-necked flask.在1L的三口燒瓶中加入大約216-224g(1.621.68 moles)的無水三氯化鋁。 While the free-flowing catalyst is stirred HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?

2、formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=10462.85 l Note1N3#Note1N3 t _self (Note 3), 81 g. (0.67 mole) of HYPERLINK /orgsyn/chemname.asp?nameID=33146 t _top acetophenone is added from the dropping funnel in

3、a slow stream over a period of 2030 minutes. 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，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 HYPERLINK /orgsyn/chemname.asp?nameID=33146 t _top acetophenone ha

4、s been added, the mixture becomes a viscous ball-like mass that is difficult to stir.當三分之一的乙酰苯被滴加，反應混合物變成一個很難攪拌的粘性的球狀團塊。 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 pr

5、oduce a temperature above 180. 然而，速度不能太快，當反應溫度超過180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 HYPERLINK /orgsyn/chemname.asp?nameID=33146 t _top acetophenone is complexed with HYPERLINK /orgsy

6、n/chemname.asp?nameID=33169 t _top aluminum chloride, ranges in color from tan to brown.當快滴加完時，團塊開始融化，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?HYPERLINK /orgsyn/chemname.asp?nameID=32917 t _top Bromine (128 g., 0.80 mole) is added dropwise to the well-stirred mixture over a period of 40 minutes HYPERLINK /Or

7、gSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=10462.85 l Note1N4#Note1N4 t _self (Note 4). 在40分鐘內在攪拌下把溴緩慢滴加到混合物中。After all the HYPERLINK /orgsyn/chemname.asp?nameID=32917 t _top bromine

8、 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蒸氣浴下攪拌1小時。 The complex is added in portions to a well-stirred mixture of 1.3 l. of cracked ice and 100 ml. of concentrated HYPERLINK /orgsyn/chemname.asp?nameID=32803 t _top hydrochloric acid in a 2-l.

9、 beaker HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=10462.85 l Note1N6#Note1N6 t _self (Note 6).反應物加入到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 ad

10、ded to the reaction flask to decompose whatever part of the reaction mixture remains there, and the resulting mixture is added to the beaker.把部分的冰水層加入到燒瓶中洗滌殘留物，然后合并到燒杯中。 The dark oil that settles out is extracted from the mixture with four 150-ml. portions of HYPERLINK /orgsyn/chemname.asp?nameID=32

11、792 t _top 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% aqueous HYPERLINK /orgsyn/chemname.asp?nameID=32850 t _top sodium bicarbonate solution, dried with anhydrous HYPERLINK /orgsyn/chemname.asp?nameID=32963 t _top sodium sulf

12、ate, 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 HYPERLINK /orgsyn/chemname.asp?nameID=32792 t _top ether is removed by distillation at atmospheric pressure, and crude 3-bromoacetophenone is stripped from a few grams of heavy dark residue by distil

13、lation 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 is carefully fractionated to obtain 94100 g.通過分餾，得到無色的流出液94-100g2、反應式：3、2-Methyl-4-ethoxalylcyclopentane-1,3,5-trione. A solution of HYPERLINK /orgsyn/chemname.asp?nameID=33215 t _top sodium ethoxide is prepa

14、red 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 HYPERLINK /orgsyn/chemname.asp?nameID=33192 t _top sodium to 950 ml. of absolute HYPERLINK /orgsyn/chemname.asp?name

15、ID=35861 t _top 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 05 in an ice bath and stirred.溶液在0-5下冰浴攪拌。 The stopper is replaced by a dropping funnel, and a cold mixture (515) of 108 g. (1.50 moles) of freshly distilled HYPERLINK /orgsyn/chemname.asp?nameID

16、=41944 t _top 2-butanone and 482 g. (3.30 moles) of HYPERLINK /orgsyn/chemname.asp?nameID=38600 t _top diethyl oxalate HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=11241.1

17、3 l Note1N1#Note1N1 t _self (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下低溫混合，在30分鐘內逐步滴加到溶液中。 After the addition is complete, the thick, orange-red mixture is allowed to warm with continued stirring to room temperature, heated under refl

18、ux 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0。The mixture is decomposed by stirring with 165 ml. of HYPERLINK /orgsyn/chemname.asp?nameID=32777 t _top sulfuric acid (1:1 by volume) added in portions.將165ml濃硫酸（體積比1:1）在攪拌加入，分解混合物。 The HYPERLINK /orgsyn

19、/chemname.asp?nameID=32963 t _top sodium sulfate formed is filtered by suction and washed with HYPERLINK /orgsyn/chemname.asp?nameID=35861 t _top ethanol (150200 ml.) HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undef

20、ined&indexvalue=1&form_change=false&time=11241.13 l Note1N2#Note1N2 t _self (Note 2). 硫酸鈉抽濾后用乙醇（150200 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 crystallization is collected by filtration, washed

21、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 140150 g.粗產(chǎn)品140-150g。 Further evaporative concentration of the mother liquor followed by cooling furnishes an additional 4050 g. of the 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

22、 total yield to 180200 g. (5359%)產(chǎn)品總共180-200g（產(chǎn)率53-59%） HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=11241.13 l Note1N2#Note1N2 t _self (Note 2). This crude material (m.p.

23、 120130) is used in the next step.粗品（熔點120130）用于下一步中 A pure sample can be obtained by crystallization from HYPERLINK /orgsyn/chemname.asp?nameID=32790 t _top ethyl acetate after treatment with HYPERLINK /orgsyn/chemname.asp?nameID=57905 t _top Norit activated HYPERLINK /orgsyn/chemname.asp?nameID=33

24、157 t _top carbon, m.p. 160162.純品是經(jīng)過活性炭處理后在乙酸乙酯中結晶得到，熔點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).在配有封閉攪拌器、滴液漏斗和冷凝回流裝

25、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 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. 燒瓶浸入冰浴中，內部溫度保持在10-20，169g（1.1mol）的磷酰氯通過滴液漏斗在15分鐘內滴加。An exother

26、mic reaction occurs with the formation of the phosphorus oxychloride - dimethylformamide complex. 放熱反應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 added to the mixture. 重新再冰浴下加

27、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. 當內部溫度降到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

28、液漏斗在1小時內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分鐘， 直到有大量氯化氫產(chǎn)生。The mixture is then cooled to 2

29、530, 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. 當混合物降溫到25-30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。The reaction mixture is again refluxed for 15 minu

30、tes, vigorous stirring being maintained all the while (Note 4). 反應物在充分攪拌下重新回流15分鐘。The cooled mixture is transferred to a 3-l. separatory funnel, and the ethylene dichloride layer is removed. 冷卻的混合物轉移到分液漏斗中，出去二氯乙烯層。The aqueous phase is extracted three times with a total of about 500 ml. of ether. 水相用

31、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- aqu

32、eous 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，蒸餾溶劑，余下的溶液移入克氏燒瓶在油浴中減壓蒸餾。The aldehyde boils at 78 at 2 mm.; there is very l

33、ittle fore-run and very little residue. 醛沸點78度在2mm；很少有預留無和殘渣。The yield of crude 2-pyrrolealdehyde is 8590 g. (8995%), as an almost water-white liquid which soon crystallizes. 當幾乎透明的液體會馬上結晶，粗品產(chǎn)量85-90g（89-95%）。A sample dried on a clay plate melts at 3540. 樣品在素燒瓷板上干燥，熔點35-40度。The crude product is purif

34、ied 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

35、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 7879% of pure 2-pyrrolealdehyde, m.p. 4445. 總得率為78-79%熔點44-45度。（1）反應式4、(1)In a 3L. round-bottomed flask HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&form

36、mode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=11475.48 l Note37N1#Note37N1 t _self (Note 1) fitted with a reflux condenser are placed 625 cc. of 95 per cent HYPERLINK /orgsyn/chemname.asp?nameID=32775 t _top alcohol HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?f

37、ormgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=11475.48 l Note37N2#Note37N2 t _self (Note 2), 500 cc. of water, 500 g. (476 cc., 4.7 moles) of pure HYPERLINK /orgsyn/chemname.asp?nameID=33095 t _top benzaldehyde HYP

38、ERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=1&form_change=false&time=11475.48 l Note37N3#Note37N3 t _self (Note 3), and 50 g. of HYPERLINK /orgsyn/chemname.asp?nameID=32881 t _top sodium cyanide (96

39、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 boiling for one-half hour HYPERLINK /OrgSyn/orgsyn/orgsyn_form.asp?formgroup=quick_form_group&dbname=orgsyn&formmode=edit&unique_id=undefined&commit_type=undefined&indexvalue=

40、1&form_change=false&time=11475.48 l Note37N4#Note37N4 t _self (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

41、 water. 在最后的30分鐘，冷卻溶液，抽濾并用少量水洗滌The yield of dry crude HYPERLINK /orgsyn/chemname.asp?nameID=33172 t _top benzoin, which is white or light yellow, is 450460 g.有450-460g白色或亮黃色的干燥的安息香。 (9092 per cent of the theoretical amount). 理論產(chǎn)率90-92%。In order to obtain it completely pure, the crude substance is re

42、crystallized from 95 per cent HYPERLINK /orgsyn/chemname.asp?nameID=32775 t _top alcohol, 90 g. of crude material being dissolved in about 700 cc. of boiling HYPERLINK /orgsyn/chemname.asp?nameID=32775 t _top alcohol; upon cooling, a yield of 83 g. of white, pure HYPERLINK /orgsyn/chemname.asp?nameI

43、D=33172 t _top 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)In a 1L. 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 i

44、ntroduction 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

45、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 45 hours by means of a water bath (Note 4). 在水浴中保持702度攪拌4-5小時。During this time hydrogen chloride is bubbled into the reaction mixture through the bent glass tube, and the excess gas is carried away through th

46、e 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- nitrobenzyl chloride begins to separate as a solid about 1 hour after the beginning of the reaction.在反應開始后的一個小時，2-羥基-5-硝基苯氯化物作為固體被分離。At the end the mixture is cooled in i

47、ce 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-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晶純化。(N

48、ote 7). The yield is 46 g. (69% based on p-nitrophenol) of a white product melting at 129130.白色產(chǎn)物46g（對硝基苯酚含69%）熔點129-130度5、B. HYPERLINK /orgsyn/chemname.asp?nameID=54757 Benzyltrans-1,3-butadiene-1-carbamate. Adry, 1-l., three-necked, round-bottomed flask is equipped with a magnetic stirring bar, a

49、thermometer, and a 250-ml., pressure-equalizing dropping funnel bearing a nitrogen inlet. The flask is flushed with HYPERLINK /orgsyn/chemname.asp?nameID=32985 nitrogenand charged with49 g. (0.50 mole) of HYPERLINK /orgsyn/chemname.asp?nameID=54761 trans-2,4-pentadienoic acid,80 g. (0.62 mole) of HY

50、PERLINK /orgsyn/chemname.asp?nameID=49477 N,N-diisopropylethylamine, and300 ml. of HYPERLINK /orgsyn/chemname.asp?nameID=33135 acetone HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N6 t _self (Note 6). The resulting solution is stirred and cooled to 0 in anicesalt bath. A solution of

51、55 g. (0.51 mole) of HYPERLINK /orgsyn/chemname.asp?nameID=35080 ethyl chloroformatein150 ml. of HYPERLINK /orgsyn/chemname.asp?nameID=33135 acetoneis added over 30 minutes while the temperature is maintained below 0 HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N7 t _self (Note 7).

52、Stirring is continued for an additional 30 minutes at 0, after which a chilled solution of65 g. (1.0 mole) of HYPERLINK /orgsyn/chemname.asp?nameID=34004 sodium azide HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N8 t _self (Note 8)in 170 ml. of water is added over a 20-minute interv

53、al, keeping the temperature below 0. The contents of the flask are stirred for an additional 1015 minutes at 0 HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N9 t _self (Note 9)and poured into a2-l. separatory funnelcontaining 500 ml. of ice-water. The acyl azide is isolated by extrac

54、tion with six250-ml. portions of HYPERLINK /orgsyn/chemname.asp?nameID=33185 toluene. The combined HYPERLINK /orgsyn/chemname.asp?nameID=33185 tolueneextracts are dried overanhydrous HYPERLINK /orgsyn/chemname.asp?nameID=34696 magnesium sulfatefor 20 minutes and concentrated to a volume ofca.300 ml.

55、 on a rotary evaporator at a water bath temperature of 4050 HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N10 t _self (Note 10).Caution! The acyl azide is potentially explosive. The solution should not be evaporated to dryness.While the HYPERLINK /orgsyn/chemname.asp?nameID=33185 tol

56、uenesolution is being concentrated, adry, 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 heating mantleis charged with43 g. (0.40 mole) of HYPERLINK /orgsyn/chemname.asp?nameID=33231 benzyl

57、 alcohol,250 mg. of HYPERLINK /orgsyn/chemname.asp?nameID=54762 4-tert-butylcatechol HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N11 t _self (Note 11), and200 ml. of HYPERLINK /orgsyn/chemname.asp?nameID=33185 toluene. About 30 ml. of toulene is distilled from the flask to remove t

58、race amounts of water, and the distillation head is replaced with a condenser fitted with a HYPERLINK /orgsyn/chemname.asp?nameID=32985 nitrogeninlet. The HYPERLINK /orgsyn/chemname.asp?nameID=33185 toluenesolution is stirred and heated at a rapid reflux under a HYPERLINK /orgsyn/chemname.asp?nameID

59、=32985 nitrogenatmosphere as the HYPERLINK /orgsyn/chemname.asp?nameID=33185 toluenesolution of the acyl azide is added over 30 minutes. The disappearance of the acyl azide and isocyanate is followed by IR analysis HYPERLINK /orgsyn/orgsyn/prepContent.asp?prep=cv6p0095 l Note1N12 t _self (Note 12).

60、Conversion to the carbamate is complete in 1030 minutes, after which the solution is cooled rapidly to room temperature by immersing the flask in anice bath. The HYPERLINK /orgsyn/chemname.asp?nameID=33185 tolueneis rapidly removed on a rotary evaporator with the water bath at 4050, producing a yell