炔键由碳链中间向末端的转移

碳链中间的炔键向末端转移的反应在昆虫性信息素及脂肪酸的合成中是一个极为有用的方法。Brown等曾报道氨基丙胺化钾(Potassium 3-amino-propylamide,KAPA)能迅速地使炔键由碳链中间移向碳链末端,产率甚佳。但该反应需用大量1,3-丙二胺,且反应时产生大量泡沫。另外,氢化钾的处理也较麻烦,所以在大量制备时存在一定的困难。最近,Macaulay用氢化钠代替氢化钾,虽然可以减少泡沫的生成,但反应仍需用大量1,3丙二胺。因此,寻找更适宜的溶剂,并减少溶剂的用量,对于大量制备有着重要的意义。

Migration of the internal triple bond of alkyn-1-ol to the terminal one with sodium hydride in 1,2-diaminopropane

Several terminal alkynols which are common intermediates for the synthesis of insect sex pheromones, are obtained by means of migration of the internal triple bond of the corresponding starting materials to the terminal one in the final products with sodium-1,2-diaminopropane prepared from sodium hydride and 1, 2-diamino-propane. Owing to the higher solubility of sodium-1, 2 -diaminopropane in 1,2-diaminopropane the use of excess amount of solvent is avoided as compared with the potassium-1, 3-diaminopropane method and the modified Brown's method. Therefore the present process should be particularly useful for large scale preparations.