药物合成复习资料第六章答案

1、第六章氧化反应习题及答案1. 根据以下指定的原料、试剂和反应条件，写出其合成反应的主要产物(1)OIICrO3CH3CO2H, 20 CCCH3SeO2CH(CH3)2(6) CH3CH2CHCCH2CH3 Mn2H2CQ4 丙酮CH3pccOHCF3CO3H(7) CH3CH=CHCO 2C2H5DMSO(8) (CH 3)2CHCH=CHCH=CHCH 2OH 一ClCOCOCl(9)H3C(12)OH3CCH3H2SO4MeOH(13)H2O2, CH3CNCH3OH, KHCO 3KMnO4丙酮(15)1) 。32) Me2S1. 根据以下指定原料、试剂和反应条件，写出其合成反应的主要

2、产物（参考答案）题号答案注释1) k2OsO3CH(CH 3)2人rVCH34OHC JCO2CH35CCH3h3xCO2CH3H3C丿CH13人。6O07OCH3CH CHCO2C2H58丿9%.）、卜HOH 2CQ0J. org. Chem., 1980, 45 : 4825.10O：HOH11cbh0OHCOONaJ. Org. Chem., 1972, 37: 3393.12H3COHCHCH3H3C 1OCH3130H14HOOC COOHJ. Org. Chem., 1974, 39: 1535.15ONlCH3歹。%本题的教材中答案可能有误？2. 在下列指定原料和产物的反应式中分

3、别填入必需的化学试剂（或反应物）和反应条件。C 二 C(CH3)2ClHHHHH CHOC二 CCH2CO2CH3CH2CO2CH3(10) H2C=CHCH(OC 2H5)2H2C CHCH(OC 2H5)2OH OHCH2O(11)4KCHCH2CH2OCPh31CHCH2CH2OCPh3CH3/CH3OOOO(12)JI11IIIIPh C CH2CH2 C -PhPh C CH-CHCPh2. 在下列指定原料和产物的反应式中分别填入必需的化学试剂（或反应物）和反应条件。（参考答案）题号答案注释11. KMnO4, H2O; 2. HCl2CrO3 (Py) 2J. Org. Chem.

4、, 1969, 34: 1979.3CrO3 (Py) 2J. Org. Chem., 1969, 34: 3587.4CrO3 (Py) 2J. Org. Chem., 1979, 44: 2441.5DMSO, Ac 2O6Org. Lett., 2003, 5: 3049.7Ag2O8J. Org. Chem., 1992, 57: 6696.9CH3COOOH, NaHCO 3J. Org. Chem., 1987, 52: 4898.10KMnO 4, H 2O, 5 C111. O3; 2. Zn, H2OJ. Org. Chem., 1972, 37: 2877.12SeO2,

5、80%AcOH (aq.)3阅读(翻译)以下有关反应操作的原文，请在理解基础上写出：(1)此反应的完整反应式(原料、试剂和主要反应条件)；(2)此反应的反应机理(历程)。 Dipyridi ne chromium(VI) oxide (Note 1).A dry, 1-1., three-necked flask fitted with a sealed mechanical stirrer, a thermometer, and a drying tube, is charged with 500 ml. of an hydrous pyrid ine (Note 2), which is

6、stirred and cooled to approximately 15 (Note 3) with an ice bath. The drying tube is periodically removed and 68 g. (0.68 mole) of an hydrous chromium(VI) oxide (Note 4) is added in portions through the neck of the flask over a 30-minute period.The chromium trioxide should be added at such a rate th

7、at the temperature does not exceed 20 and in such a manner that the oxide mixes rapidly with the pyridine and does not adhere to the side of the flask (Note 5). As the chromium trioxide is added, an intensely yellow, flocculent precipitate separates from the pyridine and the viscosity of the mixture

8、 in creases. When the additi on is complete, the mixture is allowed to warm slowly to room temperature with stirri ng. Within one hour the viscosity of the mixture decreases and the in itially yellow product cha nges to a deep red, macrocrystalli ne form that settles to the bottom of the flask whe n

9、 stirri ng is disc on ti nu ed. The supernata nt pyridi ne is deca nted from the complex and the crystals are washed several times by deca ntati on with 250-ml. porti ons of an hydrous petroleum ether. The product is collected by filtrati on on a sin tered glass funnel and washed with an hydrous pet

10、roleum ether, avoidi ng con tact with the atmosphere as much as possible. The complex is dried at 10 mm. un til it is free-flow ing,leaving 150 -60 g. (85 -91%) of dipyridine chromium(VI) oxide3 as red crystals. The product is extremely hygroscopic; con tact with moisture con verts it rapidly to the

11、 yellow dipyridi nium dichromate.4 It is stored at 0 ina brown bottle (Note 6).(2) Gen eral oxidati on procedure for alcohols.A sufficie nt qua ntityof a 5% soluti on of dipyridi nechromium(VI)oxide(Note 1) in an hydrousdichloromethane (Note 7)is prepared to provide a sixfoldmolar ratio ofcomplex to

12、 alcohol, an excessusually required for complete oxidation to the aldehyde. The freshly prepared, pure complex dissolves completely in dichloromethane at 25 at 5% cohcentration, giving a deep red solution, but solutions usually contain small amounts ofbrow n, in soluble material whe nprepared fromcr

13、udecomplex (Note 8). Thealcohol, either pure or asa soluti on in an hydrous dichlorometha ne, is added tothe red soluti on in oneportion with stirri ng at room temperature or lower. The oxidati on of unhin dered primary (and sec on dary) alcohols proceeds to completi on with in 5 to 15 minu tes at 2

14、5 with depositi on of brow ni sh-black, polymeric, reduced chromium -pyridine products (Note 9). When deposition of reduced chromium compo unds is complete (mon itori ng the react ion by GC or TLC is helpful), the super nata nt liquid is decanted from the (usually tarry) precipitate, which is rinsed

15、 thoroughly with dichloromethane (Note 10). The comb ined dichlorometha ne soluti ons may be washed with dilute hydrochloric acid, sodium hydroge n carb on ate soluti on, and water, or filtered directly through a filter aid, or passed through a chromatographic column to remove traces of pyridine and

16、 chromium salts. The product is obtained by removal of dichlorometha ne; any pyridi ne that rema ins can ofte n be removed un der reduced pressure. Hepta nal.A dry, 1-l. three-necked round-bottomed flask is equipped with a mechanical stirrer, and 650 ml. of an hydrous dichlorometha ne (Note 7) is ad

17、ded. Stirri ng is begu n and 77.5 g. (0.300 mole) of dipyridi ne chromium(VI) oxide (Note 1) is added at room temperature, followed by 5.8 g. (0.050 mole) of 1-hepta nol (Note 11) in one portion. After stirring for 20 minutes, the supernatant solution is decanted from the in soluble brow n gum, whic

18、h is washed with three 100-ml. porti ons of ether. The ether and dichlorometha ne solutio ns are comb ined and washed successively with 300 ml. of aqueous 5% sodium hydroxide, 100 ml. of 5% hydrochloric acid (Note 12), two 100-ml. portions of saturated aqueous sodium hydroge n carb on ate, and, fin

19、ally, with 100 ml. of saturated aqueous sodium chloride. The orga nic layer is dried over an hydrous magn esium sulfate, and the solve nt is removed by distillati on. Distillati on of the residual oil at reduced pressure through a small Claisen head separates 4.0 -.8 g. (70 -84%) of heptanal, b.p. 8

20、0 -84 (65 mm.), n25D 1.4094 (Note 13).3. 阅读(翻译)以下有关反应操作的原文，请在理解基础上写出：(1)此反应的完整反应式(原料、试剂和主要反应条件)；(2)此反应的反应机理(历程)。(参考答案)(1)答:cro,i + 2反应式：OOn(pyrldinch(3)答:反应式：r* (jH riilinchCl tM Clin*CHO乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱 码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码 乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码乱码