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1、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CH(CH3)2H2CrO4A丙酮PCCAMnO2CrO3(Py)2OjrCH3CH2CHCCH2CH3CH3HOCH 2cH 2cCH 2cH=CHCO 2cH 3Ch 3(6)OHCF 3c03HCH3CH=CHCO 2C2H5 (8)(CH 3)2CHCH=CHCH=CHCH 2ohDMSO .ClCOCOClH(9)HOH 2c1) 12/AcOAg/AcOH/H 2O(10)t-BuOOHMo(CO) 6*2) KOH/MeOH(13)(14)(15)2) Me 2s1)。3N OKMnO4A丙酮H
2、2O2, CH3CNCH3OH, KHCO 31.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（参考答案）题号答案注释1O2cOO3VCH3CH3)2O4OHCACO2CH35H3cccCH3；h3r/CO2CH3XoT32.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。A<Cl-(2) PhCH=CHCH 2OH 。一 6H|:C 二 C(CH3)2(4) 丁 h-H''JCH2CO2CH3CH3 OHH3CO2C -N H /、(5) cS H八0cH3 (6)QjOH0H II1 JJyl PhCH=CHCH=O%HCHO
3、一夕处CH2CO2CH3CH3 0HH3-1)S H-QCTH3 00CH3COOH 11H H CH0(8)人公""2CH(CH 3)2(9)j iQH(10) H2C=CHCH(0C 2H5)2»hX02HH C0 2H1,9/kxXr-C0NH2CH(CH 3)2H2CCHCH(0C2H5)20H 0HOOIJU(12) Ph -C-CH2CH2 C - PhOOIJll Ph - C-CH - CH - C-Ph2 .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. KMnO 4, H2O; 2.
4、HCl2CrO3 , (Py) 2J. Org. Chem., 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
5、. Chem., 1972, 37: 2877.12SeO2, 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 anhy
6、drous 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
7、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
8、 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 th
9、e 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 an
10、hydrous 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 T60 g. (85 -91%) of dipyridine chromium(VI) oxide3 as red crystals. The product is extremely hygroscopic; contact with moisture converts it rapidly t
11、o the yellow dipyridinium dichromate.4 It is stored at 0 in a brown bottle (Note 6).(2) General oxidation procedure for alcohols.A sufficient quantityof a 5% solution of dipyridinechromium(VI)oxide(Note 1) in anhydrousdichloromethane (Note 7)is prepared to provide a sixfoldmolar ratio ofcomplex to a
12、lcohol, an excessusually required for complete oxidation to the aldehyde. The freshly prepared, pure complex dissolves completely in dichloromethane at 25 at 5% con centration, giving a deep red solution, but solutions usually contain small amounts ofbrown, insoluble material whenprepared fromcrudec
13、omplex (Note 8). Thealcohol, either pure or asa solution in anhydrous dichloromethane, is added tothe red solution in oneportion 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 de
14、position 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 d
15、ichloromethane (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 prod
16、uct 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.
17、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. porti
18、ons 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 sodi
19、um 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 48 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)。(参考答案)(1)答: 反应式：cro,i + 2CrOj(pyrldinch(3)答：反应式：CrOi (jH rtilini'hClliOH CHXCIhJjtCHOCll2Ch 15