含噻二唑官能基的对叔丁基硫桥杯[4]芳烃衍生物的合成及结构

以对叔丁基硫桥杯4]芳烃(1)为原料, 在碳酸钾存在下与碘甲烷反应, 生成1,3-二取代桥杯4]芳烃(2), 其分别与1,2-二溴乙烷, 1,3-二溴丙烷在碳酸钾的存在下进行烷基化反应, 生成硫桥杯4]芳烃衍生物3和4. 在氢氧化钠存在下,其与过量的含不同官能团的2-巯基-1,3,4-噻二唑反应, 生成下缘含1,3,4-噻二唑基的硫桥杯4]芳烃衍生物5a, 5b, 6a和6b, 并通过了¹H NMR, ¹³C NMR, IR, MS和元素分析的确证. 同时, X射线分析确定了硫桥杯4]芳烃3和5a的晶体结构.

Synthesis and Structure of p-tert-Butylthiacalix[4]arene Derivatives Containing Thiadiazole Functional Moieties

The p-tert-butylthiacalix4]arene(1)was firstly alkylated with methyl iodide to obtain thiacalix4]arene(2),which was reacted with 1,2-dibromoethane and 1,3-dibromopropane to give thiacalix4]arene derivatives 3 and 4 in the presence of potassium carbonate,respectively.A series of p-tert-butylthiacalix4]arene derivatives 5a,5b,6a and 6b which append 1,3,4-thiadiazol-2-ylthio groups at the lower rims were easily synthesized in good yields by the reaction of di(bromoalkoxy)calix4]arene in-termediates 3 or 4 with 2-mercapto-1,3,4-thiadiazole derivatives in the presence of sodium hydroxide.All novel compounds were characterized by 1H NMR,13C NMR,IR,MS and elemental analysis.Meanwhile,the structures of thiacalix4]arene derivatives 3 and 5a were identified by X-ray diffraction analysis.