Ritter 反应

  • A+

碳正离子加成到腈基的氮原子上生成的腈盐加水分解得到相应的酰胺加水可以分解为酰胺。一般能产生碳正离子化合物都可以发生这类反应。由于醇或烯烃在浓硫酸或其他强酸加热条件下反应,一般在次条件下稳定的腈都可用于该类反应。

       这类反应通过腈和酸在溶剂中反应,但对于乙腈来说,直接用乙腈中应即可,对于其他较为复杂,沸点较高的底物,一般用冰醋酸稀释。

        一般卤代物用于这一反应比烯烃和醇要差,但用亚硝基四氟硼酸盐(NOBF 4 )和亚硝基六氟磷酸盐(NOPF 6 )可以室温以下反应 [5] 。这两个试剂也可直接拔除三取代碳上的氢生成碳正离子。

当使用醇作反应物时,则可以得到相应的 N-烃基酰胺

      而通过卤素或有机硒等对烯烃加成,得到的碳正性的中间体也可用于对乙腈的加成。如果所用的是环状烯烃,则为反式加成。

Ritter 反应示例一

      A solution of 5.3 g (0.1 mol ) of acrylonitrile, 50 ml of acetic acid and 7.4 g of t butylalcohol in an ice-bath was treated with conc. sulfuric acid (10.1 g, 0.1 mol) with stirring so as to keep the temperature below 40 ℃ during the addition and subsequent reaction (an hour), the reaction mixture was poured onto 200 g of ice, the product filtered and air dried, yield 10 g (yield 80 %). The product could be recrystallized from benzene.

Ritter 反应示例二

    To a mixture of alcohol (10 mmol) and trimethylsilyl cyanide (20 mmnol), cooled to - 15°C in an ice-salt bath, under nitrogen, is added concentrated sulfuric acid (30 mmol) dropwise with vigorous stirring (caution: highly exothermic). After the addition, the cold bath is removed and the mixture is stiffed at ambient temperature for 18 hrs. Tile mixture is then poured onto ice, and neutralized with 50% NaOH solution to pH = 7. The aqueous is extracted with t-BuOMe or CHCl 3 , and the combined organic extracts are washed with brine, and dried over MgSO 4 . The crude product is purified by recrystallization (solid) or flash chromatography (oil).


weinxin
我的微信
关注我了解更多内容

发表评论

目前评论:0