DESIGN, SYNTHESIS, AND PROPERTIES OF CYCLOPHANES AS HOSTS HAVING ABILITY OF FORMING INCLUSION COMPLEXES

具有形成包合物能力的主体环芳的设计、合成和性能

• 批准号: 63470126
• 负责人: KOGA Kenji
• 金额: $ 4.86万
• 依托单位: FACULTY OF PHARMACEUTICAL SCIENCES, THE UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470126/
• 关键词: Water-soluble Cyclophanes; Molecular Recognition; Diarylmethane; Inclusion Complex; Host-Guest Chemistry; Inclusion of Cationic Guests; カチオン性シクロファン; アニオン性フィクロファン; ホストゲスト錯体; クロマトグラフィー用担体; 疎水性相互作用; 電荷相互作用

Our earlier studies on cyclophanes such as QCP44 have suggested that they form inclusion complexes with anionic and neutral hydrophobic guests in aqueous solution. We intended to introduce the cyclophanes to stationary phase of column chromatography, and to design novel macrocyclic compounds as hosts for cationic guests.The skeleton of QCP44 was introduced to agarose gel with amide bond, and some structural isomers, such as 1- or 2-naphthalane sulfonic acids, could be effectively separated by the column containing this gel.Novel cyclophanes having carboxylates, ACP44 and ACP66, were synthesized, and were found to form stable 1:1 complexes with cationic guests. Stability constants (Ks) of their complexes were obtained using ^1H-NMR technique (Table 1). ACP44 exhibited the greatest value of K s for the complex with 1,4-bis(trimethylammoniummethyl)benzene. In contrast, ACP66 formed the most stable complex with 1,3-bis(trimethylammonium)propane.Investigation on novel macrocycles for selective and efficient artificial catalysts as an enzyme model is now in progress.

我们对QCP44等环烷的早期研究表明，它们在水溶液中与阴离子和中性疏水客体形成包合物。我们打算将环烷引入柱层析的固定相，并设计新的大环化合物作为阳离子客体的宿主。通过酰胺键将QCP44骨架引入琼脂糖凝胶中，可有效分离1-萘磺酸或2-萘磺酸等结构异构体。合成了含有羧酸酯ACP44和ACP66的新型环烷，并与阳离子客体形成稳定的1:1配合物。采用^1H-NMR技术得到了它们配合物的稳定常数（Ks）（表1）。ACP44与1,4-二（三甲基铵甲基）苯配合物的K s值最大。相比之下，ACP66与1,3-二（三甲基铵）丙烷形成最稳定的配合物。以酶为模型的新型选择性高效人工催化剂的研究正在进行中。

项目成果

Kenji Koga: "Cyclophanes as Hosts for aromatic and Aliphatic Guests" J. Inclusion Phenomena, 7, 53-60, 1989.

Kenji Koga：“环芳烷作为芳香族和脂肪族客体的宿主”J. Inclusion Phenomena，7, 53-60, 1989。

Kenji Koga: "Cyclophanes as Hosts for Aromatic and Aliphatic Guests" Journal of Inclusion Phenomena. 7. 53-60 (1989)

Kenji Koga：“环芳烷作为芳香族和脂肪族客体的宿主”包容现象杂志。

古賀憲司: ""分子認識能を有する純人工ホスト化合物の開発と応用","包接化合物の基礎と応用",戸田芙三夫監修" エヌ・ティ-・エス, 32 (1989)

Kenji Koga：“具有分子识别能力的纯人工主体化合物的开发和应用”，“包合物的基础和应用”，Fuzo Toda 监督，NTS，32（1989）

小田嶋和徳: Chem.Pharm.Bull. 37. (1989)

小田岛和典：Chem.Pharm.Bull 37。（1989）

Kazunori Odashima: "Molecular Recognition and Discrimination of Hydrophobic Guests in Water by Quaternary Ammonium cyclophanes Having Diarylmethane" Chemical and Pharmaceutical Bulletin. 37. 257-259 (1989)

Kazunori Odashima：“含有二芳基甲烷的季铵环烷对水中疏水客体的分子识别和辨别”化学和制药通报。