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

本工作是利用二硫键可逆裂解合成轮烷。在这三年中，取得了许多重要的发现。在该合成方法中，哑铃形二硫化物与硫醇反应，引起二硫化物键的可逆裂解，在此过程中，轮分子滑入二硫化物键中，生成相应的轮烷。本工作的目的之一是完善合成方法，该方法可用于多种[2]和[3]轮烷的高收率合成。通过精确的热力学控制，收率最高可达95%。我们把这个方法命名为“进入法”。同时，得到的[2]轮烷具有两个铵基团，其中一个铵基团被冠醚轮覆盖，当满足一定条件时，轮组分可以从一个铵基团自由移动到另一个铵基团，称为“穿梭”。采用^1H NMR方法研究了取代基对冠醚轮的影响，发现取代基的给电子能力越大，洗牌速率越快。作为该合成方法在聚轮烷合成中的应用，以双功能铵盐和冠醚为原料合成了聚[3]轮烷。结果表明，在一定催化量的噻吩存在下，仅将两种双功能组分混合，就得到了mw30000的[3]轮烷。卟烷作为单体单元的连接结构具有拓扑连通性，而由此制备的聚[3]轮烷是第一种拓扑聚合物。通过工作完成了新的合成方法“进入法”，实现了[2]和[3]轮烷的高收率合成，并将模具法应用于双功能单体上获得了第一个拓扑聚合物。

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.