Synthesis and functionalization of novel unsaturated thiacrown ethers and related compounds

新型不饱和硫杂冠醚及相关化合物的合成与功能化

• 批准号: 12640523
• 负责人: SHIMIZU Toshio
• 金额: $ 2.37万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640523/
• 关键词: Organic sulfur compound; Cyclic unsaturated compound; Crown ether; Thiacrown ether; Mercury complex; Crystal structure; Redox behavior; チオクラウンエーテル; 銀錯体; 紫外吸収スペクトル

The 6-, 9-, 12-, 15-, 18-, 21-, 24-, and 27-membered unsaturated thiacrown ethers were synthesized by reacting cis-dichloroethene with sodium sulfide in acetonitrile. The crystal structures were determined by X-ray crystallography, and it was found that there are cavities in these molecules. The reactions of 18- and 21-membered unsaturated thiacrown ethers, 18-UT-6 and 21-UT-7, with CF_3COOAg in acetone afforded novel silver(I) complexes Ag^1(18-UT-6)(CF_3COO) and Ag^1_2(21-UT-7)(CF_3COO)_2, respectively. The stoichiometry for complexation of 15-UT-5, 18-UT-6, and 21-UT-7 with CF_3COOAg in solution was examined by ^1H NMR measurement. The titration plots of 15-UT-5 and 21-UT-7 showed a distinct break point at the 1:1 and 2:1 metal/macrocycle ratio, respectively, while the plots of 18-UT-6 gradually changed at the range of 1:1-2:1. From these results, 15-UT-5 and 21-UT-7 were found to include selectively one and two silver ions, respectively, and 18-UT-6 showed low selectivity for the inclusion number. The complexation of 18-UT-6 with 1 equiv of HgCl_2 in acetone afforded mercury complex Hg^<11>(18-UT-6)Cl_2. The complexations of 18-membered saturated thiacrown ether, 18S6, with 1 equiv of each HgCl_2 and CdCl_2 in acetone afforded Hg^<11>(18S6)Cl_2 and Cd^<11>(18S6)Cl_2, respectively. The crystal structure of Hg^<11>(18-UT-6)Cl_2 revealed that the mercury atom was inside the cavity of the macrocycle and the geometry around the mercury atom was an eight-coordinate hexagonal bipyramidal arrangement. ORTEP drawing of Hg^<11>(18S6)Cl_2 revealed the existence of mercury atom outside the cavity of the ring. ^1H NMR study of Hg^<11>(18-UT-6)Cl_2 in acetone-d_6 indicated that the interconversion between free 18-UT-6 and pure complex was slower than the NMR time scale. The titration experiment by ^1H NMR revealed that 18-UT-6 had inclusion selectivity for the number of mercury atoms.

在乙腈中，顺式二氯乙烯与硫化钠反应，合成了6、9、12、15、18、21、24和27元不饱和硫代冠醚。用X射线晶体学方法测定了它们的晶体结构，发现分子中存在空穴。18-和21-元不饱和硫代冠醚18-UT-6和21-UT-7与CF_3COOAg在丙酮中反应，分别得到了新的银配合物Ag^1（18-UT-6）（CF_3COO）和Ag^1_2（21-UT-7）（CF_3COO）_2。用~ 1H NMR测定了15-UT-5、18-UT-6和21-UT-7与CF_3COOAg在溶液中络合的化学计量比。15-UT-5和21-UT-7的滴定曲线分别在1：1和2：1金属/大环比率下显示出明显的断点，而18-UT-6的滴定曲线在1：1-2：1的范围内逐渐变化。根据这些结果，发现15-UT-5和21-UT-7分别选择性地包含一个和两个银离子，并且18-UT-6显示出对包含数的低选择性。18-UT-6与1当量HgCl_2在丙酮中络合生成汞配合物Hg^<11>（18-UT-6）Cl_2。18元饱和硫代冠醚18 S6分别与1当量的HgCl_2和CdCl_2在丙酮中络合生成Hg^<11>（18 S6）Cl_2和Cd^<11>（18 S6）Cl_2。Hg^<11>（18-UT-6）Cl_2的晶体结构表明，汞原子位于大环的空腔内，汞原子周围的几何构型为八配位六方双锥结构。对Hg^<11>（18 S6）Cl_2的ORTEP作图揭示了汞原子在环腔外的存在。Hg 18<11>-UT-6-Cl 2在丙酮-d 6中的~ 1H NMR研究表明，游离态18-UT-6与纯配合物的相互转化比NMR时间慢。用~ 1H NMR进行的滴定实验表明，18-UT-6对汞原子数具有包结选择性。

项目成果

Tsuchiya, T., Shimizu, T., Kamigata, N.: "Unsaturated Thiacrown Ethers : Synthesis, Physical Properties, and Formation of a Silver Complex"Journal of the American Chemical Society. 123(47). 11534-11538 (2001)

Tsuchiya, T.、Shimizu, T.、Kamigata, N.：“不饱和硫冠醚：合成、物理性质和银络合物的形成”美国化学会杂志。

Shimizu, T., Kawaguchi, M., Hirabayashi, K., Kamigata, N.: "Synthesis and Structures of 15-and 18-Membered Unsaturated Selenacrown Ethers and Their Complexation with Silver Trifluoroacetate"Organic Letters. (in press).

Shimizu, T.、Kawaguchi, M.、Hirabayashi, K.、Kamigata, N.：“15 和 18 元不饱和硒冠醚的合成和结构及其与三氟乙酸银的络合”有机快报。

Shimizu, T., Kawaguchi, M., Hirabayashi, K., kamigata, N.: "Synthesis and Structures of 15- and 18-Membered Unsaturated Selenacrown Ethers and Their Complexation with Silver Trifluoroacetate"Organic Letters. in press.

Shimizu, T.、Kawaguchi, M.、Hirabayashi, K.、kamigata, N.：“15 和 18 元不饱和硒冠醚的合成和结构及其与三氟乙酸银的络合”有机快报。

Tsuchiya, T., Shimizu, T., Hirabayashi, K., Kamigata, N.: "Silver Complexes with Unsaturated Thiacrown Ethers : Inclusion Behavior of Conformationally Restricted Macrocycles"The Journal of Organic Chemistry. 67(19). 6632-6637 (2002)

Tsuchiya, T.、Shimizu, T.、Hirabayashi, K.、Kamigata, N.：“具有不饱和硫冠醚的银络合物：构​​象限制性大环化合物的包合行为”有机化学杂志。

Tsuchiya, T., Shimizu, T., Hirabayashi, K., kamigata, N.: "Silver Complexes with Unsaturated Thiacrown Ethers: Inclusion Behavior of Comformationally Restricted Macrocycles"The Journal of Organic Chemistry. 67 (19). 6632-6637 (2002)

Tsuchiya, T.、Shimizu, T.、Hirabayashi, K.、kamigata, N.：“含不饱和硫冠醚的银配合物：构象限制性大环化合物的包合行为”有机化学杂志。