双冠醚化合物的合成研究 Ⅲ.一类新的双冠醚的合成

Studies on Synthesis of Biscrown Ether Compounds Ⅲ.Synthesis of Some New Bi-Ccrown Ethers

邻苯二酚、3,5-二叔丁基邻苯二酚分别与1,5-二氯-3-氧(杂)戊烷在碱性条件下反应,合成了开链冠醚化合物(1a—b)。1a—b与环氧氯丙烷在氢氧化钠正丁醇中缩合,得到相应的6-羟基二苯并-16-冠-5(2a—b)。化合物2a—b分别与丁二酰氯、壬二酰氯在无水苯中反应,生成了两种新的酯型双冠醚化合物3a—b;2a—b分别与1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,8-二氯-3,6-二氧(杂)辛烷及1,11-二氯-3,6,9-三氧(杂)十一烷在无水二氧六环中反应,得到了四种新的醚型双冠醚化合物4a—e。

The open chain crown 1a—1b have been conveniently Synthesized from the reaction of catechol, 3, 5-di-t-butyl-catechol with 1, 5-di-chloro-3-oxapentane under basic condition respectively. Condensation of 1a—1b with epichorohydrin gave 6-hydroxyldibenzo-16-crown-5 compounds 2a—2b. Two new biserown ether esters 3a—3b were obtained by the reaction of 2a—2b with suceinic and nonanedioyl chlorides in anhydrous benzene respectively. Reaction of 2a—2b with various α, ω-dihalides gave four new bisorown ethdr compouds 4a—4e cenneeted by ether linkage.