A solution of sodium ethoxide(乙醇盐)

A solution of sodium ethoxide(乙醇盐) is prepared from 60 g. (2.6 mol) clean sodium and 700 ml of absolute alcohol (dried over calcium oxide or sodium) in a 2000 ml round-bottomed flask(烧瓶) equipped with a reflux(逆流) condenser(冷凝器). To the hot solution added a mixture of 234g (2 moles) of pure benzyl cyanide 264g (3 moles) of dry ethyl acetate (dried by refluxing(回流冷却) over P2O5 for 30min followed by distillation(蒸馏)). The mixture is thoroughly shaken, the condenser closed with a calcium chloride tube, and the solution heated on the steam bath for two hours before standing overnight. The next morning the mixture is stirred with a wooden rod to break lumps, cooled in a freezing mixture to -10癈, and kept at this temperature for two hours. The sodium salt is collected on a 6 inch Buchner funnel(漏斗) and washed four times on the funnel with 250 ml portions of ether. The filter cake is practically colorless(无色的) and corresponds 250-275g of dry sodium salt, or 69-76% of the calculated mount. The combined filtrates(滤液) are placed in the freezing mixture until they can be worked up as indicated below.

The sodium salt still wet with ether is dissolved(溶解) in 1.3 liters of distilled(净化的) water at room temperature, the solution cooled to 0癈, and the nitrile(腈) precipitated(沉淀) by adding slowly, with vigorous(有力的) shaking, 90 ml of glacial(冰的) acetic(醋的) acid, while the temperature is kept below 10癈. The precipitate separated by suction filtration and washed four times on the funnel with 250 ml portions of water. The moist cake weighing about 300g corresponds to 188-206g (59-64%) of dry colorless alpha-phenylacetoacetonitrile, mp 87-89癈.

Phenyl-2-Propanone [2]


350 ml of concentrated sulfuric(硫磺的) acid is placed in a 3000ml flask and cooled to -10癈. The total first crop of moist alpha-phenylacetoacetonitrile obtained according to the procedure above (corresponding to 188-206g or 1.2-1.3 moles of dry product) is added slowly, with shaking, the temp being kept below 20癈 (If pure dry alpha-phenylacetoacetonitrile is used, half its weight of water should be added to the sulfuric acid or charring will take place on the steam bath). After all is added the flask is warmed on the steam bath until solution is complete and then for five minutes longer. The solution is cooled to 0癈, 1750ml of water added rapidly, and the flask placed on a vigorously boiling water bath and heated for two hours, with occasional shaking. The ketone(酮) forms a layer and, after cooling, is separated and the acid layer extracted with 600ml of ether. The oil and ether layers are washed successively(相继地) with 100ml of water, the ether combined with the oil and dried over 20g of anhydrous(无水的) sodium sulfate. The sodium sulfate is collected on a filter, washed with ether, and discarded(抛弃). The ether is removed from the filtrates, and the residue distilled from a modified Claisen flask with a 25 cm fractionating(分别) side arm. The fraction boiling at 110-112癈 at 24 mmHg is collected; it weighs 125-150g (77-86% of the theoretical amount).

結果 (中文) 1:

钠 ethoxide(乙醇盐) 解决方案是配备 reflux(逆流) condenser(冷凝器) 2000 毫升圆底 flask(烧瓶) 编写从 60 g.(2.6 mol) 清洁钠和无水乙醇 （干过氧化钙或钠） 700 毫升。到热解决方案添加混合 234 g （2 摩尔） 的纯苄氰化物 264 g （3 摩尔） 的干乙酸乙酯 （干由 refluxing(回流冷却) 在 P2O5 为 30 分钟，接着由 distillation(蒸馏))。混合物是从根本上动摇，凝汽器关闭与氯化钙管和加热蒸汽浴缸的水龙头前一夜之间站两个小时的解决方案。第二天早上，用木杖 — — 打破搅拌混合物肿块，冷却冻结混合物-10癈，和在此温度下保持两个小时。钠盐是收集关于布氏 funnel(漏斗) 6 英寸和洗上漏斗与醚 250 毫升部分的四倍。滤饼实际上是 colorless(无色的) 和对应 250-275 克的干钠盐或计算山 69-76%。结合的 filtrates(滤液) 放在冻结的混合物直到他们可以白手起家创建了如下所示。湿用乙醚的钠盐仍是 dissolved(溶解) 在 1.3 升的 distilled(净化的) 水在室温下冷却到 0癈和 nitrile(腈) precipitated(沉淀) 通过添加慢慢地，用颤抖的 vigorous(有力的)，90 毫升的 glacial(冰的) acetic(醋的) 酸，而温度是低于 10癈的解决方案。沉淀抽滤分离和 250 毫升的水部分漏斗洗四次。重约 300 克的滤饼对应于干无色 mp 87 89癈 α-phenylacetoacetonitrile 188-206 克 （59-64%)。苯基-2-丙酮，[2]350 毫升的集中的 sulfuric(硫磺的) 酸是放置在 3000 毫升瓶，并冷却到-10癈。潮湿的阿尔法 phenylacetoacetonitrile 得出以上 （对应于 188 206 g 或 1.2-1.3 痣的干燥产品） 过程总的第一批颤抖，被保持在 20癈以下 （如果使用纯干阿尔法 phenylacetoacetonitrile，体重一半的水应加入硫酸或炭化上会发生蒸汽浴室） 的温度缓慢，加入。毕竟被添加烧瓶加热蒸汽浴缸的水龙头直到解决方案是完整的然后为五分钟的时间。溶液冷却到 0癈，1750 毫升的水迅速，补充和烧瓶放在大力沸水浴和加热两个小时，偶尔晃动。Ketone(酮) 形成一层，冷却后，分离和酸层用 600 毫升的醚萃取。石油醚层洗了 100 毫升的水与 successively(相继地) 的醚结合油和干超过 20 克的 anhydrous(无水的) 硫酸酯钠盐。硫酸钠被收集在筛选器中，用乙醚和 discarded(抛弃) 清水洗净。从滤液中移除醚和渣蒸馏从 25 厘米 fractionating(分别) 侧臂改性克莱森瓶子里。收集了沸腾在 110-112癈在 24 毫米汞柱的分数;它的重量 125 150 g （理论量的 77-86%)。