Generalization of New Synthetic Methods of Macrocyclic compounds Utilizing Characteristic Bonding Properties of Hypervalent Atom and Their Applications

我们报道了利用高价硫的特殊成键性质合成新型大环化合物的新方法。结果总结如下：1)2，3-二甲基四氮杂硫并戊烯衍生物(1)与1当量反应。对二甲苯二异硫氰酸酯在回流苯中反应得到大环化合物2，其中含有两个四氮杂并戊烯骨架。2)分子中有两个戊二烯环的化合物3与对二甲苯二异硫氰酸酯反应得到大环化合物4，其中有四个四氮杂硫戊烯环，这些环以层状形式存在。3)3与3，6，9-三氧十一烷-1，11-二异硫氰酸酯反应得到大环化合物5，其中含有低聚乙二醇链和戊二烯两个环。4)通过还原消除高价硫，2，4和5分别与NaBH_4反应生成了26-35元的扩环大环6，7和8。5)用氢氧化钾水溶液处理2，4和5，分别得到4045元大环化合物9，10和11，它们都含有硫脲部分，C=S；6)大环化合物6-8是H_2PO_4的阴离子受体。这些反应将为大环化合物的研究提供有用的方法。

We report new methods for the synthesis of novel macrocyclic compounds by utilizing characteristic bonding properties of hypervalent sulfur. The results are summarized as follows: 1)Treatment of 2,3-dimethyltetraazathiapentalene derivative (1)with 1 equiv. of p-xylilene diisothiocyanate in refluxing benzene gives the macrocyclic compound 2 which has two tetraazathiapentalene skeletons in the compound. 2)The reaction of compund 3 which has two pentalene rings in the molecule with p-xylilene diisothiocyanate affords macrocyclic compound 4 which has four tetraazathiapentalene rings, these rings being situated in a laminate form. 3)The reaction of 3 with 3,6,9-trioxaundecane-1,11-diisothiocyanate affords macrocyclic compound 5 which has having two rings containing oligoethyleneglycol chain and pentalene ring. 4)The reaction of 2,4 and 5 with NaBH_4 gives ring-expanded 26-35-membered macrocycles 6,7 and 8, respectively, via the reductive elimination of hypervalent sulfur. 5)Treatment of 2,4 and 5 with aqueous potassium hydroxide gives 4045 membered macrocyclic compound 9, 10 and 11, respectively, which have thiourea moieties via the elimnation of C=S^<IV> moiety. 6) The macrocyclic compound 6 -8 serve as an anionm receptor for H_2PO_4. The reactions described here would provide the useful methods for the variety of macrocyclic compounds.