Synthesis and Application of New Host Molecules derived from Macrocycles.

大环化合物新宿主分子的合成及应用。

• 批准号: 11305063
• 负责人: NISHIMURA Jun
• 金额: $ 15.08万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11305063/
• 关键词: crownether; cyclophane; catenane; fullerene; calixarene; receptor; ionophore; high selectivity; 高選択性; クラウノファン; γ-シクロデキストリン; 液-液抽出実験; 重金属イオン; [2+2]光環化反応; スチレン誘導体; ポリエーテル環; キラル分子; 臭化物; パラフェニレン; 立体障害; カップリング反応; 鈴木反応; クラウン化合物; クラウノパドラン

1. Double armed crownophanes were successfully synthesized. They showed the high ion selectivity for silver ion. Crownophanes containing amino group were also synthesized with cyclodextrin in water by photocycloaddition. Catenanes including[2]- and [3] catenanes were successfully synthesized by using ion-dipole interaction with crownether.2. The product distribution of [60]fullerene bisadducts was investigated by the different two methods. The benzyne method exclusively gave cis-1 form. All racemates (trans-2, trans-3, and cis-3) were successfully resolved into each enantiomer by using chiral HPLC column chromatography. Bisadducts attaching crownether moiety showed the unique ion selectivity for alkali metalions.3. Calixarenes having some ethyl acetate units were successfully synthesized. They showed the good extractability for alkali metal ions. When the number of the ethylacetate unit decreased, the extractability for larger ions like Rb^+ and Cs^+ gradually decreased. They were successfully converted to dendrimer type molecules with amino alcohol.

1. 成功合成了双臂冠状啡。它们对银离子有很高的选择性。在水中以环糊精为原料，采用光环加成法制备了含氨基的冠诺芬。利用离子偶极相互作用，与冠状醚成功合成了[2]-和[3]链烷。用两种不同的方法研究了[60]富勒烯双合物的产物分布。苯法只得到顺式-1。所有外消旋物（反式-2、反式-3和顺式-3）通过手性高效液相色谱柱层析成功地分解成每个对映体。二加糖对碱金属离子具有独特的选择性。成功地合成了含有乙酸乙酯单元的杯芳烃。对碱金属离子具有良好的可萃取性。随着乙酸乙酯单元数的减少，对Rb^+、Cs^+等较大离子的可萃取性逐渐降低。它们在氨基醇的作用下成功转化为树突状分子。

项目成果

Y. Okada: "A Synthesis and Characterization of New Chiral Calix[4]arenes"Enantiomer. 7. 93-106 (2002)

Y. Okada：“新手性杯[4]芳烃的合成和表征”对映体。

Y. Nakamura: "Synthesis and Fluorescence Emission Behavior of anti-[2.3](3,10)Phenanthrenophane : Overlap between Phenanthrene Rings Required for Excimer Formation"Chem. Lett.. 970-971 (2001)

Y. Nakamura：“抗[2.3](3,10)菲芬烷的合成和荧光发射行为：准分子形成所需的菲环之间的重叠”Chem。

Y. Nakamura: "Langmuir and LB Films of Amphiphilic [60]Fullerene Derivatives"Bull. Chem. Soc. Jpn.. 73. 1615-1619 (2000)

Y. Nakamura：“两性 [60] 富勒烯衍生物的 Langmuir 和 LB 薄膜”公牛。

Y. Okada: "New Caixcrown-type Ionophores Derived from All Possible Regioisomers of Rigid Calix[4]arene"Synlett. 41-44 (2000)

Y. Okada：“源自刚性杯[4]芳烃所有可能的区域异构体的新Caix冠型离子载体”Synlett。

Y. Hayashida: "Synthesis and Structure of Novel [2.n](4,4')Binaphthylophanes : A New Family in Cyclophane Chemistry"Tetrahedron Lett.. 40. 6435-6438 (1999)

Y. Hayashida：“新型 [2.n](4,4)联萘芬的合成和结构：环芳化学中的新家族”Tetrahedron Lett.. 40. 6435-6438 (1999)