药物合成 复习资料 第六章答案.doc

《药物合成反应》（第三版） 闻韧主编 第六章氧化反应习题及答案 PAGE PAGE 5 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. 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 1 2 3 4 5 6 7 8 9 J. org. Chem., 1980, 45：4825. 10 11 J. Org. Chem., 1972, 37: 3393. 12 13 14 J. Org. Chem., 1974, 39: 1535. 15 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别填入必需的化学试剂（或反应物）和反应条件。 2. 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. HCl 2 CrO3·(Py) 2 J. Org. Chem., 1969, 34: 1979. 3 CrO3·(Py) 2 J. Org. Chem., 1969, 34: 3587. 4 CrO3·(Py) 2 J. Org. Chem., 1979, 44: 2441. 5 DMSO, Ac2O 6 Org. Lett., 2003, 5: 3049. 7 Ag2O 8 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 st