Development of Novel Synthetic Method of Rotaxane by Utilizing Dynamic Property of SS Linkage and Its Application to Molecular Materials

利用SS键动态性质开发轮烷新合成方法及其在分子材料中的应用

• 批准号: 12440181
• 负责人: TAKATA Toshikazu
• 金额: $ 7.94万
• 依托单位: Osaka Prefecture University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440181/
• 关键词: disulfide bonding; rotaxane synthesis; crown ether; poly[3]rotaxane; entering method; topological bonding; secondary ammonium salt; thermodynamic control; [2]ロタキサン; [3]ロタキサン; 可逆的結合-再開裂; 熱力学的安定性; 全平衡; 二官能性クラウンエーテル; ポリロタキサン; 可逆的開裂 再結合

This work was to synthesize rotaxanes by utilizing reversible cleavage of disulfide linkage. During these three years, many important findings have been done. In the synthetic method, dumbbell-shaped disulfide reacts with thiol to give rise to the reversible cleavage of the disulfid bond during which wheel molecule slips into the disulfide bond to yield the corresponding rotaxane. One of the purposes of this work was to complete the synthetic method and the method was actually useful in the syntheses of many [2] and [3]rotaxanes in high yields. The highest yield reached 95% via precise thermodynamic control. We have named mis method "entering method".Meanwhile, in the case of [2]rotaxane obtained which has two annmonium groups one of which was covered with crown ether wheel, the wheel componet can move freely from one ammonium moiety to another one when some conditions are fulfilled, that is known as "shuttling". Effect of substituents on the crwon ether wheel was studied by ^1H NMR method, and the shuffling rate was enhanced as the electron-donating power of the substituents increased. As an application of the synthetic method to the synthesis of polyrotaxane, poly[3]rotaxane was synthesized with bifunctional ammonium salt and crwon ether. As a result, first ply[3]rotaxane with MW 30000 was obtained only by mixing the two bifunctional components in the presence of a catalytic amount of thiophenol. The poryrotaxane had topotogical lilnkages as the linking structure of the monomer units, while the poly[3]rotaxane thus prepared was the first topological polymer.The novel synthetic method "entering method" was completed through the work which enabled the high yield syntheses of [2] and [3] rotaxanes, and the first topological polymer was obtained by applying die method to the bifunctional monomers.

本工作是利用二硫键的可逆断裂来合成轮烷。在这三年中，取得了许多重要的发现。在合成方法中，哑铃形二硫键与硫醇反应以引起二硫键的可逆断裂，在此期间轮分子滑入二硫键以产生相应的轮烷。本工作的目的之一是完善合成方法，该方法实际上可用于许多[2]和[3]轮烷的高产率合成。通过精确的热力学控制，最高收率达到95%。同时，在文献[2]中得到的具有两个铵基的轮烷中，其中一个被冠醚轮覆盖，当满足一定条件时，轮组可以自由地从一个铵基移动到另一个铵基，这就是所谓的“穿梭”。用~ 1H NMR方法研究了取代基对螺旋醚轮的影响，发现随着取代基给电子能力的增加，螺旋醚轮的洗牌速率增加。作为该合成方法在聚轮烷合成中的应用，以双官能度铵盐和交联醚为原料合成了聚[3]轮烷。结果，仅通过在催化量的苯硫酚的存在下混合两种双官能组分，获得MW 30000的第一层[3]轮烷。聚[3]轮烷是第一种拓扑聚合物，通过对[2]和[3]轮烷的高产率合成，完成了新的合成方法“进入法”，并将其应用于双官能团单体，得到了第一种拓扑聚合物。

项目成果

Yoshio Furusho: "Chemical Modification of Amide-Based Catenanes and Rotaxanes I. Synthesis of secondary Amine [2]Catenanes and [2] Rotaxanes by the Borane Reduction of secondary Amide [2]Catenanes and [2]Rotaxanes and Mobility of Their Components"Bull.Che

Yoshio Furusho：“基于酰胺的索烷和轮烷的化学改性 I. 通过仲酰胺 [2] 索烷和 [2] 轮烷的硼烷还原合成仲胺 [2] 索烷和 [2] 轮烷及其组分的迁移率”

Yow-hei Sohgawa: "Polyslipping: A New Approach to Polyrotaxane-like Assemblies"Cthm.Lett.. 774-775 (2001)

Yow-hei Sohkawa：“Polyslipping：一种聚轮烷类组装的新方法”Cthm.Lett.. 774-775 (2001)

Yoshio Furusho: ""Unlock-Lock" Approach to [2] and [3] Rotaxanes : Entering of a Ring through disulfide Linkage That is Unlocked by Thiol "Key""Chem.Lett.. 2000. 18-19 (2000)

Yoshio Furusho：“[2]和[3]轮烷的“解锁-锁定”方法：通过硫醇“钥匙”解锁的二硫键进入环”Chem.Lett.. 2000. 18-19 (2000)

T. Takata: "Design of Functions of Nano-Materials by Synthesis of Interlocked Molecules"Kobunshi (High Polymer). 50. 770-773 (2001)

T. Takata：“通过合成互锁分子来设计纳米材料的功能”Kobunshi（高分子）。

Y. Furusho: "Future Polymers - Current Studies on Polyrotaxanes and Polycatenanes"Kino Zairyo (Functionalized Materials). 20[12]. 19-27 (2000)

Y. Furusho：“未来聚合物 - 聚轮烷和聚链烷的最新研究”Kino Zairyo（功能化材料）。