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

在这份报告中，我们描述了一种利用高价硫的特殊成键性质合成大环化合物的新方法。2，3-二甲基四氮硫杂五烯衍生物(1)与1当量。二异硫氰酸酯类化合物在苯中回流反应24小时，得到具有两个四氮杂并戊烯骨架的大环化合物(2)，产率较高。(2)在二甲基亚砜中与NaBH_4在室温下反应24小时，得到开环大环化合物(3)，其中含有四个硫脲基团。经X-射线单晶分析确证了(3)的结构。用乙醇-KOH水溶液处理(2)得到开环大环化合物(4)，通过消除C=S^&lt；IV&gt；；部分，环上具有四个硫脲部分。含对二甲苯单元的大环化合物(3)和(4)是CH3COO~-和H_2PO_4~-的阴离子受体。以反式偶氮苯为间隔基团的大环只有效地捕获CH3COO^-。然而，光照射产生的顺式异构体并不作为阴离子受体。

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.