Development of Novel method for Synthesizing Macrocyclic Compounds Utilizing Characteristic Bonding properties of Hypervalent Sulfur

在本报告中，我们描述了利用高价硫的特征键性质合成大环化合物的新方法。2,3 -二甲基四氮杂二烯衍生物(1)与1等量的二异硫氰酸酯衍生物在回流苯中处理24h，得到具有两个四氮杂二烯骨架的大环化合物(2)，收率高。(2)与NaBH_4在DMSO中室温反应24h，得到开环大环化合物(3)，该化合物环中含有4个硫脲基团。x射线晶体学分析证实了(3)的对二甲苯结构。(2)用乙氧基氢氧化钾水溶液处理，通过消除C=S^<IV>部分，得到环上有四个硫脲基团的开环大环化合物(4)。具有对二甲苯单元的大环化合物(3)和(4)是CH_3COO^-和H_2PO_4^-离子的阴离子受体。以反式偶氮苯为间隔单元的大环只捕获CH_3COO^-。然而，光照射产生的顺式异构体不能作为阴离子受体。

In this report, we describes the novel method for synthesizing macrocyclic compounds utilizing characteristic bonding properties of hypervalent sulfur. Treatment of 2, 3 - dimethyltetraazathiapentalene derivative (1) with 1 equiv. of diisothiocyanate derivatives in refluxing benzene for 24h gives the macrocyclic compounds (2) with two tetraazathiapentalene skeletons in good yield. The reaction of (2) with NaBH_4 in DMSO at room temperature for 24h affords the ring-opened macrocyclic compound (3) that contains four thiourea moieties in this rings. The structure of (3) with p-xylylene unit is confirmed by X-ray crystallographic analysis. The treatment of (2) with an aqueous EtOH-KOH solution gives the ring-opened macrocyclic compound (4) having four thiourea moieties in the ring by the elimination of the C=S^<IV>moiety. The macrocyclic compounds (3) and (4) having p-xylylene unit serves as anion receptor for CH_3COO^- and H_2PO_4^- ions. The macrocycles having trans-azobenzene unit as spacer capture efficiently only CH_3COO^-. However, the cis isomer which produced by the light irradiation does not serve as anion receptor.