由硝基化合物合成醛酮

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 用碱处理脂肪族硝基化合物,使其成为氮酸盐,然后在酸性条件下进行水解,可得醛或酮,这就是 Nef 反应。其缺点是不常用于带有抗酸或抗碱能力弱的基团的化合物。

       对 Nef 反应的改进则是在比较缓和的情况下使用各种氧化剂,常用于酮的合成。所用的氧化剂有 KMnO 4 ,TiCl 3 , NaNO 2 -nPrONO, O 3 , t-BuOOHV(acac) 2 ,MoO 5 等。收率均很高。

由硝基化合物合成醛酮反应示例 1

    t-BuOH (10 ml) was added to 0.1 g (2.5 mmol) of NaH under nitrogen atmosphere and stirred for 10 min. 0.245 g (1 mmol) of tert-butyl 2,2,3,3-tetramethyl-4-nitrobutanoate in 10ml of t-BuOH was then added to the solution. 1 min later, 200 ml of cool pentane was added,followed by 25 g of ice/water and 0.115 g (0.73mmol) of KMnO 4 in 40 ml of cooled water. The mixture was vigorously stirred for 10 min. 1ml of 1 M solution of NaHS 2 O 2 and 2 ml 1M H 2 SO 4 was added. Organic phase was seperated and washed with water, brine and dried over MgSO 4 , concentrated to give 0.95 g of tert-butyl 2,2,3,3-tetramethyl-4-oxobutanoate.Yield: 91%

、由硝基化合物合成醛酮反应示例 2 :

    KOH (0.56 g, 0.01 mol) and dicyclopropyl(nitro)methane (0.71 g 0.005 mol) was added to 100 ml of water. MgSO 4 (4.8g, 0.04 mol) in 400 ml of water was added under stirring. The mixture was cooled to 0℃. KMnO 4 (1.1 g, 0.007 mol) solution was added. The reaction mixture was extracted with ether for 3 times. Ether phase was dried over MgSO 4 , concentrated to give dicyclopropylmethanone (yield: 81%).

由硝基化合物合成醛酮反应示例 3 :

    Methanolic sodium methoxide is prepared by cautiously adding small pieces of freshly cut sodium (5.67 g., 0.247 g.-atom) to 200 ml. of cold methanol in a 500-ml., three-necked flask equipped with a mechanical stirrer, a 50-ml. addition funnel, and a condenser fitted with a nitrogen-inlet tube. The resulting solution is stirred and cooled in an ice bath while 38.6 g. (0.243 mole) of 5-nitroheptan-2-one is added over 15 minutes, after which stirring is continued for another 15 minutes at 0°. The ice bath is then replaced with an acetone–dry ice bath, the nitrogen-inlet tube and addition funnel are removed, and a fritted-glass dispersion tube is inserted into the solution. With continued cooling and vigorous stirring, an ozone–oxygen mixture is bubbled through the solution for 5 hours.

    After ozone generation has been stopped, pure oxygen is passed through the reaction mixture, removing excess ozone. Dry ice cooling is continued while 21 g. (0.34 mole) of dimethyl sulfide is added in one portion, and the mixture is then allowed to come to ambient temperature overnight (18 hours). Methanol is removed with a rotary evaporator, and the residual liquid is dissolved in 250 ml. of diethyl ether. This solution is percolated through a  short mat of silica gel (50 g.), removing polar impurities, then concentrated with a rotary evaporator, leaving a residue which is stirred with 30 ml. of 5% hydrochloric acid for 45 minutes. Chloroform (40 ml.) is added, the organic layer is separated, and the aqueous phase is further extracted with two 30-ml. portions of chloroform. The organic extracts are combined, washed with saturated aqueous sodium hydrogen carbonate, dried over anhydrous sodium sulfate, filtered, and concentrated with a rotary evaporator. Vacuum distillation of the residue with a Kugelrohr apparatus gives 22.7 g. (73%) of 2,5-heptanedione。



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