The dichlorocarbene generation reaction from CHCl3 and solid KOH in CH2Cl2 was catalyzed by the p-t-butylcalix[6]arene derivative 1 which bears six 3,6,9-trioxadecyl substituents on the phenolic oxygens. Dichlorocarbene generated by this method reacted efficiently with alkenes and amides to give dichlorocyclopropane derivatives and nitriles, respectively, in high yields. The reaction with alkadiene having isolated double bonds gave mixtures of the mono- and bis-dichlorocarbene adducts, but the monoadduct formation always predominated. The catalytic action of the calixarene and the reactivity features of dichlorocarbene generated by the above procedure are discussed on the basis of kinetic measurements. They are also compared with those of the 18-crown-6-catalyzed reactions.
由
CHCl3和固体KOH在
CH2Cl2中催化生成二
氯碳烯的反应是由具有六个3,6,9-三氧
十烷取代基的p-叔丁基大环[6]
芳烃衍
生物1催化的。通过这种方法生成的二
氯碳烯与烯烃和酰胺反应,分别高产率地生成二
氯环丙烷衍
生物和腈类物质。与具有孤立双键的烯烃二烯的反应生成单个和双二
氯碳烯加成物的混合物,但单加成物的生成总是占主导地位。基于动力学测量,讨论了大环
芳烃的催化作用以及上述过程中生成的二
氯碳烯的反应特性,并与
18-冠-6催化反应的特性进行了比较。