Synthesis of Dye-Bridged Crown Ether-Cyclodextrin Dyads and Their "Class-Selective" Coloration for Amines

染料桥联冠醚-环糊精二元体的合成及其胺的“类选择性”着色

• 批准号: 11640582
• 负责人: KANEDA Takahiro
• 金额: $ 0.83万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640582/
• 关键词: crown ether; permethylated cyclodextrin; amine indicator; molecular recognition; azo dye; シクロデキストリン

Like the essential roles of tosylates in the CD chemistry, the corresponding permethylated tosylates and monoalcohols are, undoubtedly, of great value as starting materials for making various amphiphilic and lipophilic CD derivatives, such as amines, esters, ethers, halides, and sulfides. Therefore, a facile preparative method for such intermediates is desired. We were able to establish a new practical method based on a new 20 g-scale direct permethylation reaction for the preparation of versatile 6-O-monotosyl and 6-monohydroxy permethylated α-, β-, and γ-cyclodextrins in good yields The present permethylation technique with a NaH-MeI combination is applicable to other polyhydroxy compounds with NaI-susceptible substituents.The first [5] supercy clodextrin whose nano-sized cyclo-pentameric array is held only by a mechanical bond was syn-thesized by the pentakis-azo coupling of a new hermaphrodite monomer with 2-naphthol as a stopper, isolated by chroma-tography, and characterized by MS, 2D NMR, and Vis spectral methods with the help of computer simulation. The chemical architecture has the following characteristics : (1) it is the first example of [n]SCDs constructed with s-mode insertion ; (2) it enables the termination at a molecular hierarchy with α-D-glucopyranose as the bottom ; (3) it is a nano-sized, condensed and lipophilic pentagon with a diameter of 3.9 nm and a thickness of 1.9 nm.In order to judge whether the self-association to face-to-face or cyclic dimers is a general or special phenomenon, we have designed and synthesized new lipophihc monomers composed of a permethylated α-cyclodextrin as host, an azobenzene moiety as internal guest and aρ-xylylene spacer inserted between the two. The synthesis of the two monomers and their self-association to stable lipophilic face-to-face dimmers are described.

与对甲苯磺酸盐在CD化学中的重要作用一样，相应的全甲基化对甲苯磺酸盐和一元醇无疑是制备各种两亲性和亲油性CD衍生物的重要原料，如胺、酯、醚、卤化物和硫化物。因此，需要一种简便的制备方法来制备这类中间体。我们建立了一种新的基于20g规模的直接过甲基化反应的新的实用方法，用于制备通用性强的6-O-单糖和6-单羟基过甲基化α-，β-和γ-环糊精，产率很高。本方法结合NaH-MeI的全甲基化技术适用于其他具有NaI敏感取代基的多羟基化合物。第一个仅通过机械键连接纳米级环五聚体的[5]超环糊精是通过以2-萘酚为塞子的新型两性单体的五偶氮偶联反应合成的，并用MS，2D，NMR进行了表征和可见光光谱方法，并借助计算机模拟。这种化学结构具有以下特点：(1)它是第一个以S模式插入构建的[n]SCD的例子：(2)它能够在以α-D-葡萄糖为底层的分子层次上终止；(3)为判断环状二聚体与面对面或环状二聚体的自缔合是普遍现象还是特殊现象，我们设计并合成了以全甲基化的α-环糊精为主体、偶氮苯为内客体、ρ-二甲苯为间隔基的新型亲脂单体。描述了这两种单体的合成及其与稳定的亲脂性面对面二聚体的自缔合作用。

项目成果

Takahiro Kaneda, Takashi Yamada, Tatsuhiko Fujimoto, and Yoshiteru Sakata: "The First [5] Supercyclodextrin whose Cyclopentameric Array is Held Only by a Mechanical Bond"Chemistry Letters. No.12. 1264-1265 (2001)

Takahiro Kaneda、Takashi Yamada、Tatsuhiko Fujimoto 和 Yoshiteru Sakata：“第一个 [5] 环五聚阵列仅由机械键保持的超级环糊精”化学快报。

Tatsuhio Fujimoto, Yukihiro Uejima, Hiroya Imaki, Naoya Kawarabayashi, Jong Hwa Jung, Yoshiteru Sakata, and Takahiro Kaneda: "The First Lipophilic Face-to-Face Dimers of Permethylated α-Cyclodextrin-Azobenzene Dyads through a p-Xylylene Spacer"Chemistry L

Tatsuhio Fujimoto、Yukihiro Uejima、Hiroya Imaki、Naoya Kawarabayashi、Jong Hwa Jung、Yoshiteru Sakata 和 Takahiro Kaneda：“通过对二甲苯间隔基实现全甲基化 α-环糊精-偶氮苯二联体的第一个亲脂性面对面二聚体”Chemistry L

兼田隆弘: "環状5量体構造が機械的結合のみによって保たれている最初の[5]スーパーシクロデキストリン"ケミストリーレターズ(日本化学会速報誌). 1264-1265 (2001)

Takahiro Kaneda：“第一个仅通过机械键维持环状五聚体结构的[5]超级环糊精”化学快报（日本化学会通报）1264-1265（2001）。

Takahiro Kaneda, Tatsuhiko Fujimoto, Jun'ichiro Goto, Kaori Asano, Yoshitaka Yasufuku, Jone Hwa Jung, Chiaki Hosono, and Yoshiteru Sakata: "New Large-Scale Preparations of Versatile 6-O-Monotosyl and 6-Monohydroxy Permethylated α-,β-, and γ-Cyclodextrins"

Takahiro Kaneda、Tatsuhiko Fujimoto、Junichiro Goto、Kaori Asano、Yoshitaka Yasufuku、Jone Hwa Jung、Chiaki Hosono 和 Yoshiteru Sakata：“多功能 6-O-单酰基和 6-单羟基全​​甲基化 α-,β 的新型大规模制备-、γ-环糊精"

Tatsuhiko Fujimoto: "The First Lipophilic Face-to-Face Dimers of Permethylated α-Cyclodextrin-AzobenzeneDyads through a p-Xylylene Spacer"Chemistry Letters. 5号. 564-565 (2000)

Tatsuhiko Fujimoto：“通过对二甲苯间隔基实现全甲基化 α-环糊精-偶氮苯二元体的第一个亲脂性面对面二聚体”《化学快报》第 5 期。564-565 (2000)