Application of use "unclassical nucleophilic aromatic substitution" protocol to thiacalixarene derivatives for developing novel functional materials

应用“非经典亲核芳香取代”方案在硫代杯芳烃衍生物中开发新型功能材料

• 批准号: 13450361
• 负责人: IKI Nobuhiko
• 金额: $ 9.47万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450361/
• 关键词: thiacalixarene; calixarene; nucleophilic aromatic substitution; functional material; crystal structure; inclusion; conformational behavior; metal complex; 配座平衡; 溶媒抽出

Aminothiacalixarenes, new members of the thiacalixa[4]arene (TCA) family having amino functions at the lower rim, were prepared from sulfur-oxygenated derivatives of TCA by applying the chelation-assisted nucleophilic aromatic substitution (S_NAr) reaction to estimate their intrinsic abilities for developing novel functional materials.1.Selective syntheses of tetraamino, 1,2-and 1,3-diamino, and monoamino TCAa were achieved by using the S_NAr reaction on tetra-O-methylsulfonyl-and sulfinylcalix[4]arenes by lithium amides as the key step. Conformational analysis of the substrates indicated that the methoxy groups in a cis relationship with at least one adjacent sulflinyl group selectively underwent the S_NAr reaction.2.Inclusion behavior of tetraamino TCA was investigated by crystallizing the host molecule from a series of solvents. It was found that the compound selectively formed 1:1 complexes with acetonitrile and dichloromethane. The acetonitrile complex adopted a cone conformation, while the host molecule crystallized out in a 1,3-alternate information from methanol without forming any inclusion complex, indicating that the complexation was accompanied by the conformational change of the host molecule (induced fit to the guest molecule).3.Complexation ability of tetraamino TCA was investigated by solvent extraction experiments. It was found that tetraamino TCA served as a highly specific extractant for Au(III) and Pd(II) ions. The X-ray crystallographic analysis of a Pd(II) complex indicated that tetraamino TCA ligated is the metal ion with the bridging sulfur atoms and deprotonated amino functions. On the other hand, 1,2-diamino TCA was found to flexibly ligate to soft and hard metal ions by changing the ligation site (NH_2,OH).4.Derivatization of the amino TCAs gave tetra(N-ethoxycarbonylmethyl) and bis(salicylideneamino) derivatives. The amino groups of amino TCAs were displaced with iodine atoms via the diazonium salts.

本论文以硫代杯[4]芳烃（TCA）为原料，通过螯合辅助的亲核取代反应（S_NAr）合成了氨基硫代杯[4]芳烃（TCA），探讨了它们作为新型功能材料的潜力。以四-O-甲磺酰基杯[4]芳烃和亚磺酰基杯[4]芳烃为原料，通过氨基锂的S_NAr反应，合成了四-O-甲磺酰基杯[4]芳烃和单氨基杯[4]芳烃。底物构象分析表明，甲氧基与至少一个相邻的亚磺酰基呈顺式关系，选择性地进行了S_NAr反应。2.通过在一系列溶剂中结晶，研究了四氨基TCA的包结行为。发现该化合物与乙腈和二氯甲烷选择性地形成1：1的络合物。乙腈络合物呈锥形构象，而主体分子以1，3-交替信息方式从甲醇中结晶出来，没有形成任何包合物，表明络合过程伴随着主体分子构象的变化（诱导拟合到客体分子）。结果表明，四氨基TCA对Au（III）和Pd（II）离子具有高度的选择性萃取作用。X-射线晶体学分析表明，四氨基TCA配位的钯（II）配合物是金属离子与桥接硫原子和去质子化的氨基功能。另外，1，2-二氨基TCA通过改变连接位点（NH_2，OH），可以灵活地与金属离子和金属离子形成连接。4.氨基TCA衍生化得到四（N-乙氧羰基甲基）和双（水杨醛氨基）衍生物。氨基TCA的氨基通过重氮盐被碘原子取代。

项目成果

F.Narumi: "Proximal O, O'-capped calix[4]arenes with a disiloxane bridge as highly efficient synthetic intermediates for 1,2-dialkylation at the lower rim."Tetrahedron Lett.. 43(4). 621-625 (2002)

F.Narumi：“带有二硅氧烷桥的近端 O, O 封端的杯 [4] 芳烃作为下缘 1,2-二烷基化的高效合成中间体。”Tetrahedron Lett.. 43(4)。

F.Narumi: "First synthesis of 25,26-bridged thiacalix[4]crowns by the use of a 25,26-O-disiloxanediyl-capped p-tert-butylthiacalix[4]arene."J.Chem.Soc., Perkin Trans.. 1,(16). 1843-1844 (2002)

F.Narumi：“通过使用 25,26-O-二硅氧烷二基封端的对叔丁基 thiacalix[4] 芳烃首次合成 25,26-桥联 thiacalix[4] 冠。”J.Chem.Soc.,

N.Kon: "Inclusion behavior of water-soluble thiacalix-and calix[4]arenes towards substituted benzenes in aqueous solution."Org.Biomol.Chem.. 1(4). 751-755 (2003)

N.Kon：“水溶性硫杂杯芳烃和杯[4]芳烃对水溶液中取代苯的包合行为。”Org.Biomol.Chem.. 1(4)。

宮野荘太郎, 他: "多彩な可能性を秘めた新規ホスト化合物 -チアカリックスアレーン-"日本化学会誌. 2001・11. 609-622 (2001)

Sotaro Miyano 等人：“一种具有多种可能性的新主体化合物 -Thiacalixarene”，日本化学学会杂志 2001/11（2001）。

T.Hattori, Y.Shimazumi, H.Goto, O.Yamabe, N.Morohashi, W.Kawai, S.Miyano: "Synthesis, Resolution, and Absolute Stereochemistry of (-)-Blestriarene C."J.Org.Chem.. 68(6). 2099-2108 (2003)

T.Hattori、Y.Shimazumi、H.Goto、O.Yamabe、N.Morohashi、W.Kawai、S.Miyano：“(-)-Blestriarene C 的合成、解析和绝对立体化学”J.Org.Chem