制备二氮杂冠醚和三氮杂冠醚的新方法  

A New Method for the Synthesis of Diaza and Triaza Crown Ethers

作　　者：王德粉[1] 蒋立建[2] 龚雁 胡宏纹[1] 

机构地区：[1]南京大学化学系 [2]南京铁道医学院化学教研室

出　　处：《高等学校化学学报》1989年第2期148-152,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：以糖精为原料合成二氮杂冠醚和三氮杂冠醚。使糖精与二甘醇或三甘醇二氯化物和N,N-二(β-氯乙基)丁胺的DMF溶液在少量碘化钾存在下烃化、氨解,再用二甘醇或三甘醇的二对甲苯磺酸酯烃化生成保护的冠醚环。后者与20％盐酸作用除去保护基生成游离的环体。此法合成路线短原料价廉易得。二氮杂18-冠-6总产率37％左右。In this paper a new method for the synthesis of di- and tri-aza crown ethers starting from saccharin is reported. Saccharin is first alkylated with di-or tri-ethylene glycol dichloride and N,N-(β-chloroethyl) butyl amine in DMF solution in the presence of small amount of potassium iodide. The N-alkylated saccharin is treated with ammonia and transformed into the N-alkylated o-carbamoyl benzene sulfonamide, which is then alkylated once again with ditosylates of di- and tri-ethylene glycol to form the crown ethers on the imino groups protected with o-carbamoyl benzene sulfonyl group. Di- and triaza crown ethers are obtained by removing the protective group on the nitrogen with 20% hydrochloric acid. By this method, are prepared 10 new intermediates, which can be used to synthesize di- and tri-aza crown ethers bridged by like or different chains. The total yield of 1 ,10-diaza-18-crown-6 amounts to 36% close to that by the high dilution method starting from 1, 8-diaza-3,7-dioxaoctane. Compared with the methods reported in the literature, the features of the new method are. (1) using cheap starting materials (2) the o-carbamoyl benzene sulfonyl protective groups can be removed more easily than tosyl group.

关 键 词：二氮杂冠醚 三氮杂冠醚 制备 糖精 

分 类 号：O623.423[理学—有机化学]