Photochemical synthesis of new ionophores and their application

新型离子载体的光化学合成及其应用

• 批准号: 08555226
• 负责人: NISHIMURA Jun
• 金额: $ 6.85万
• 依托单位: GUNMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08555226/
• 关键词: [2+2]photocycloaddition; styrene derivertives; oligo(oxyethylene)linkage; crown compounds; crownophanes; lithiophilic ionophores; extraction; silver metal ion; クラウン化合物; クラウノファン; クラウノパドラン; リチウムイオン選択性; ナトリウムイオン選択性; アザクリプトファン; ホストーゲスト化学; トリビニル

We have developed intramolecular [2+2] photocycloaddition of styrene derivatives, such as substituted styrene, vinylnaphthalene, vinyiphenanthrene, and so on. The photocyclization showed tether-length dependency ; i.e., the longer the tether becomes, the lower yield is obtained. If oligo(oxyethylene) linkage is used as the tether, however, the yield does not depend on the length and generally becomes quantitative. This tendency has been determined to be due to the flexible property of oligo(oxyethylene) chain.We were prompted to use this efficient reaction to make a new type of crown compounds (so- called crownophanes) and succeeded in the cultivation of a new ionophore synthetic method.The prototypical crownophanes showed relatively high Li^+ ion selectivity on the solid-liquid extraction, so we tried to improve the selectivity and found, after several trials, that simply and appropriately modified crownophanes having two cyclobutane linkages (crownopaddlanes) extracted the Li ion exclusively and quantitatively on the extraction experiment.Next we tried to make crownophanes working efficiently for the extraction of heavy metal cations. We first made some precursors having two hydroxyl groups on the oligo(oxyethylene) linkage or the aromatic nuclei and then treated these functional groups with pyridylmethyl chloride. The modified crownophanes with two pyridine side arms showed high affinity toward Ag^+ ion on the liquid-liquid extraction. Especially, the compound having the side arms on the aromatic nuclei exhibited the excellent selectivity.

我们已经发展了苯乙烯衍生物的分子内[2+2]光环加成反应，如取代苯乙烯、乙烯基萘、乙烯基菲等，其光环化反应表现出链长依赖性，即，系绳变得越长，获得的产量越低。然而，如果使用寡聚（oxidase）键作为系链，则产率不依赖于长度，并且通常是定量的。这种趋势已被确定是由于低聚物的柔性性质我们被提示利用这种高效的反应来制备一种新型的冠醚化合物（crownophanes），并成功地培育了一种新的离子载体合成方法。原型crownophanes对固-液萃取显示出相对较高的Li^+离子选择性，因此我们试图提高选择性，并发现，经过几次实验，简单而适当地改性的具有两个环丁烷键的冠芳（crownopaddlane）在萃取实验中对Li离子进行了专门和定量的萃取，接下来我们试图使冠芳有效地用于萃取重金属阳离子。我们首先制备了一些在低聚（氧代）键或芳核上具有两个羟基的前体，然后用吡啶甲基氯处理这些官能团。在液-液萃取过程中，两个吡啶侧臂修饰的冠芳对Ag^+离子表现出很高的亲和性。特别是，在芳核上具有侧臂的化合物表现出优异的选择性。

项目成果

M.Taki 他4名: "Synthesis of Polyesters Containing[60]Fullerene Moiety in the Main Chain by Mild Surface Condensation Method" Polym.J.29. 1020-1022 (1997)

M.Taki 等 4 人：“通过温和表面缩合法合成主链中含有[60]富勒烯部分的聚酯”Polym.J.29 (1997)。

S.-R.Gao, S.Inokuma, and J.Nishimura: "Selective Ion Clefts Based on a Three-Bridged[43]Cyclophane" J.Inclusion Phenomena. 23・4. 329-341 (1996)

S.-R.Gao、S.Inokuma 和 J.Nishimura：“基于三桥[43]环烷的选择性离子裂隙”J.Inclusion Phenomena 23・4 (1996)。

M.Taki 他6名: "Selective Functionalization on[60]Fullerene Governed by Tether Length" J.Am.Chem.Soc.109. 926-932 (1997)

M.Taki 和其他 6 人：“由系链长度控制的[60]富勒烯的选择性功能化”J.Am.Chem.Soc.109 (1997)。

M.Taki: "Synthesis of Polyesters Containing[60]Fullerene Moiety in the Main Chain by Mild Surface Condensation Method" Polym.J.29. 1020-1022 (1997)

M.Taki：“通过温和表面缩合法合成主链中含有[60]富勒烯部分的聚酯”Polym.J.29。

Y.Okada他3名: "New Ionophores Derived from a Rigid Calixarene Regioisomer" Tetrahedron Lett.(in press). (1999)

Y. Okada 和其他 3 人：“来自刚性杯芳烃区域异构体的新离子载体”Tetrahedron Lett。（出版中）。