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键合特性合成新型大环化合物的新方法。结果表明：1)在回流苯中，用1等量的对二甲苯二异硫氰酸酯处理2,3-二甲基四氮杂二烯衍生物(1)，得到具有两个四氮杂二烯骨架的大环化合物2。2)分子中含有2个戊二烯环的化合物3与对二甲苯二异硫氰酸酯反应生成具有4个四氮杂二烯环的大环化合物4，这些环呈层状。3与3,6,9-三氧十一烷-1,11-二异硫氰酸酯反应得到具有双环的大环化合物5，该化合物具有低聚乙二醇链和戊二烯环。4) 2、4和5与NaBH_4反应，通过还原消除高价硫，分别得到扩展环的26-35元大环6,7和8。5)用氢氧化钾水溶液处理2,4和5，分别得到4045元的大环化合物9,10和11，它们通过消除C=S^<IV>片段而具有硫脲基团。6)大环化合物6 -8作为H_2PO_4的阴离子受体。本文所描述的反应将为各种大环化合物的合成提供有用的方法。

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.