新的酚型开链冠醚及由其衍生的二苯并冠醚的合成

将水杨醛与碱和氯甲基甲基醚反应, 再经过NaBH4还原, 即制得邻(甲氧基甲氧基)苯甲醇, 然后将其在DMF中与NaH和二(或三)甘醇二对甲苯磺酸酯反应, 得开链冠醚1a和1b。1a和1b经稀酸水解, 即脱保护而分别生成新的酚型开链冠醚2a和2b。用2a与二甘醇二对甲苯磺酸酯和NaH在DMF溶液中反应, 合成顺型二苯并-20-冠-6(3); 而2a与环氧氯丙烷在NaOH水溶液中反应, 则合成了17-羟基二苯并-18-冠-5(4)。

Synthesis of new phenolic type acyclic crown ethers and derived dibenzocrown ethers

In the presence of NaH and in DMF, the acyclic crown ethers 1a and 1b were synthesized by the reaction of di - or triethyleneglycol ditosylate and o - methoxymethoxybenzyl alcohol, which was obtained from salicylaldehyde via the protection of the hydroxyl group with chloromethyl methyl ether followed by the reduction of the formyl group with NaBH4. The hydrolysis of 1a and 1b with dilute hydrochloric acid provided the diphenolic type acyclic crown ethers 2a and 2b respectively in good yield. By using 2a as the intermediate, syn - dibenzo - 20 - crown -6(3) was produced by reaction with diethyleneglycol ditosylate and NaH in DMF solution, and 17 - hydroxydibenzo - 18 -crown - 5(4) was obtained by reaction with epichlorohydrin and NaOH in aqueous solution.