药物合成反应(闻韧_第三版)第六章课后答案

第六章 氧化反应习题及答案1. 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产物(1)32o CrO 3(2)CCH 3O SeO 2(3)H 2CrO 4OH3CH(CH 3)2丙酮(4)HOCH 2CH 22CH=CHCO 2CH 3CH 3CH 3PCC(5)CO 2CH 332(6)CH 3CH 2CHCCH 2CH 3OMnO 2(7)CH 3CH=CHCO 2C 2H 5CF 3CO 3H(8)(CH 3)2CHCH=CHCH=CHCH 2OHDMSO(9)OHHOH 2C6(10)O222) KOH/MeOH武汉工程大学化工与制药学院(11)2) NaOHCOOH(12)OH 3CH 3HH 3C H 2SO 4(13)H 2O 2, CH 3CN 33(14)KMnO 4(15)NO322. 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。

(1)ClCH 3ClCOOH(2)PhCH=CHCH 2OHPhCH=CHCH=O(3)O(4)C H2CO 2CH 3H C(CH 3)2HC HCH 2CO 2CH 3H C H CHO(5)CH H 3CO 2C CH H 3CO 2C (6)OHOCH 3OOCH 3(7)2H(8)CONH 2CH(CH 3)2CONH 2CH(CH 3)2O(9)OHOH(10)H 2C=CHCH(OC 2H 5)2H 2CCHCH(OC 2H 5)2OH OH(11)CH2CHCH2CH2OCPh3CH3OCHCH2CH2OCPh3CH3(12)Ph OCH2CH2OPh Ph COCH CHOPh2. 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1 1. KMnO4, H2O; 2. HCl2 CrO3·(Py) 2 J. Org. Chem., 1969, 34: 1979.3 CrO3·(Py) 2J. Org. Chem., 1969, 34: 3587.4 CrO3·(Py) 2J. Org. Chem., 1979, 44: 2441.5 DMSO, Ac2O6 Org. Lett., 2003, 5: 3049.7 Ag2O8 J. Org. Chem., 1992, 57: 6696.9 CH3COOOH, NaHCO3 J. Org. Chem., 1987, 52: 4898.10 KMnO4, H2O, 5℃11 1. O3; 2. Zn, H2O J. Org. Chem., 1972, 37: 2877.12 SeO2, 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）。

(1) Dipyridine chromium(VI) oxide (Note 1).A dry, 1-l., three-necked flask fitted with a sealed mechanical stirrer, a thermometer, and a drying tube, is charged with 500 ml. of anhydrous pyridine (Note 2), which is 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 anhydrous 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 that 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 increases. When the addition is complete, the mixture is allowed to warm slowly to room temperature with stirring. Within one hour the viscosity of the mixture decreases and the initially yellow product changes to a deep red, macrocrystalline form that settles to the bottom of the flask when stirring is discontinued. The supernatant pyridine is decanted from the complex and the crystals are washed several times by decantation with 250-ml. portions of anhydrous petroleum ether. The product is collected by filtration on a sintered glass funnel and washed with anhydrous petroleum ether, avoiding contact with the atmosphere as much as possible. The complex is dried at 10 mm. until it is free-flowing,leaving 150–160 g. (85–91%) of dipyridine chromium(VI) oxide3 as red crystals. The product is extremely hygroscopic; contact with moisture converts it rapidly to the yellow dipyridinium dichromate.4 It is stored at 0° in a brown bottle (Note 6).(2) General oxidation procedure for alcohols.A sufficient quantity of a 5% solution of dipyridine chromium(VI) oxide (Note 1) in anhydrous dichloromethane (Note 7) is prepared to provide a sixfold molar ratio of complex to alcohol, an excess usually required for complete oxidation to the aldehyde. The freshly prepared, pure complex dissolves completely in dichloromethane at 25° at 5% concentration, giving a deep red solution, but solutions usually contain small amounts of brown, insoluble material when prepared from crude complex (Note 8). The alcohol, either pure or as a solution in anhydrous dichloromethane, is added to the red solution in one portion with stirring at room temperature or lower. The oxidation of unhindered primary (and secondary) alcohols proceeds to completion within 5 to 15 minutes at 25° with deposition of brownish-black, polymeric, reduced chromium–pyridine products (Note 9). When deposition of reduced chromium compounds is complete (monitoring the reaction by GC or TLC is helpful), the supernatant liquid is decanted from the (usually tarry) precipitate, which is rinsed thoroughly with dichloromethane (Note 10). The combined dichloromethane solutions may be washed with dilute hydrochloric acid, sodium hydrogen carbonate solution, and water, or filtered directly through a filter aid, or passed through a chromatographic column to remove traces of pyridine and chromium salts. The product is obtained by removal of dichloromethane; any pyridine that remains can often be removed under reduced pressure.(3) Heptanal.A dry, 1-l. three-necked round-bottomed flask is equipped with a mechanical stirrer, and 650 ml. of anhydrous dichloromethane (Note 7) is added. Stirring is begun and 77.5 g. (0.300 mole) of dipyridine chromium(VI) oxide (Note 1) is added at room temperature, followed by 5.8 g. (0.050 mole) of 1-heptanol (Note 11) in one portion. After stirring for 20 minutes, the supernatant solution is decanted from the insoluble brown gum, which is washed with three 100-ml. portions of ether. The ether and dichloromethane solutions are combined 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 hydrogen carbonate, and, finally, with 100 ml. of saturated aqueous sodium chloride. The organic layer is dried over anhydrous magnesium sulfate, and the solvent is removed by distillation. Distillation of the residual oil at reduced pressure through a small Claisen head separates 4.0–4.8 g. (70–84%) of heptanal, b.p. 80–84° (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）。