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通过卤代物消除制备烯烃

烯烃化合物是含碳碳双键的一类化合物,因其双键的不饱和性,可以发生多种类型的氧化或者还原反应,构建出各种其他官能团,因而在有机化学中占有非常重要的地位,是合成各种化合物的重要中间体。



通过卤代物消除制备烯烃



邻位碳上有氢原子的脂肪烃是很容易发生β消除生成烯烃的,如果用一级碱来消除会伴随取代反应的副产物,这种情况用高位阻的碱能提高消除产率。(P. Veeragu, R. T. Arnold, and E. W. Eigemann, J. Am. Chem. Soc.86, 3072 (1964); R. A. Bartsch and J. F. Bunnett, J. Am. Chem. Soc., 90, 408 (1968).)




实例一


Amixture of 0.4 g (0.8 mmol) of compound Aand 2 ml of piperidine was heated for 10 h at 110°C. The solvent was distilledoff under reduced pressure, the residue was dissolved in 50 ml of methylenechloride, the solution was washed with water and dried over MgSO4, the solvent was removed, and the residue was crystallized from ethanol to give P 0.28 g.

Reference: Russ.J.Org.Chem2012, 48, 957-967.

实例二


DibromideI, 5.0 g (18 mmol), was added to a solution of 0.99 g (43 mmol) of metallic sodium in 70 ml of ethanol. The mixture was heated for 1 h under reflux, the solvent was removed under reduced pressure, and the residue was treated with250 ml of water and extracted with ethyl acetate. The extract was dried overanhydrous Na2SO4, filtered, and evaporated under reduced pressure, and the residue was distilled in a vacuum. Yield 54%, colorless transparent viscous liquid. bp 70-90°C (4 mm).

Reference: Russ.J.Org.Chem2013, 49, 1329-1334.



来源:览博网



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