Quantitative Synthesis and Function Development of Macrocycles Based on Slow Deprotection Self-polycondensation and Dynamic Covalent Chemistry

基于慢脱保护自缩聚和动态共价化学的大环化合物的定量合成和功能开发

• 批准号: 22655037
• 负责人: MATSUMOTO Toshihiko
• 金额: $ 2.03万
• 依托单位: Tokyo Polytechnic University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2010
• 资助国家: 日本
• 起止时间: 2010 至 2011
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-22655037/
• 关键词: 高分子合成; 超分子化学; 動的共有結合化学; 大環状分子

Mechanism for the quantitative formation of a macrocycle Cm6(cyclic hexakis(m-phenyleneimine)) from m-aminobenzaldehyde diethylacetal via water-initiated slow-deprotection polycondensation was investigated using MALDI-TOF MS and SEC. The reversibility in formation-cleavage of imine linkage, that is dynamic covalent chemistry, and.-staking interaction between flat Cm6 molecules had played a significant role in the quantitative formation. A variety of imine-type macrocycles having a functional group were successfully prepared using this method, which was found to be a potential protocol for the macrocycle synthesis. Mutual conversion between the macrocycle and the soluble linear polymers having a wide range of molecular weights by a heat stimulus was observed. The collapse-regeneration of the macrocycle was a reversible process. A mixture of two kinds of macrocycles gave a complex containing each building block. With the aid of an iminomethylene-type analogue Cm6H, which was readily prepared by the hydride-reduction of imine linkage in Cm6, a fullerene C_<60> was dissolved in a polar solvent like DMSO. Indigo carmine and new coccine dyes were precipitated from the acid solutions by addition of Cm6H.

采用MALDI-TOF MS和SEC研究了间氨基苯甲醛二乙缩醛水引发缓慢脱保护缩聚反应生成大环化合物Cm 6（环六（间苯亚胺））的机理。亚胺键形成-断裂的可逆性，即动态共价化学，以及Cm 6平面分子间的相互作用在定量形成中起着重要作用。利用该方法成功地合成了一系列含功能基的亚胺类大环化合物，为大环化合物的合成提供了一条新的途径。通过热刺激，观察到大环和具有宽范围分子量的可溶性线性聚合物之间的相互转化。大环的再生是一个可逆过程。两种大环化合物的混合物得到一个包含每个构件的配合物。利用Cm 6中亚胺键的顺式还原反应制备亚氨基亚甲基型类似物Cm 6 H，将富勒烯C_6<60>溶解在极性溶剂DMSO中。通过加入Cm 6 H从酸溶液中沉淀出靛蓝胭脂红和新的胭脂红染料。

项目成果

π-Stacked Precipitation-driven Cyclization and Mutual Conversion between Linear Poly(m-phenylene imine)s and the Macrocycle

线性聚间亚苯基亚胺与大环之间的π堆积沉淀驱动环化及相互转化

• 发表时间: 2011
• 作者: Toshihiko Matsumoto;Saori Sugaya;Sho Hasegawa
• 通讯作者: Sho Hasegawa

Quantitative Synthesis of m-Phenylene Imine Macrocycles Based on p-Stacked Precipitation-Driven Cyclization and Reversible Interchange of Linear Oligomers

基于对位堆积沉淀驱动环化和线性低聚物可逆交换的间亚苯基亚胺大环化合物的定量合成

• 发表时间: 2010
• 作者: T.Matsumoto;K.Ishida;S.Oishi
• 通讯作者: S.Oishi

Selective macrocycle synthesis based on π-stacked precipitation-priven cyclization and reversible interchange of linear oligomers

基于π堆积沉淀阻止环化和线性低聚物可逆交换的选择性大环合成

• 发表时间: 2010
• 作者: Toshihiko Matsumoto;Kozo Ishida;Seitaro Oishi
• 通讯作者: Seitaro Oishi

らせんフォルダマーを経由するm-フェニレンイミン鎖状オリゴマーの沈澱駆動環化と鎖-環相互変換

间苯亚胺线性低聚物通过螺旋折叠体的沉淀驱动环化和链环互变

• 发表时间: 2011
• 作者: 長谷川翔;松本利彦;松本利彦;松本利彦
• 通讯作者: 松本利彦

Quantitative Synthesis of Highly Shape-anisotropic and Persistent Phenyleneimine Macrocycles Based on Reversible Interchange of Linear Polymers

基于线性聚合物可逆交换的高形状各向异性和持久性苯亚胺大环化合物的定量合成

• 发表时间: 2010
• 作者: T.Matsumoto;K.Ishida;S.Oishi
• 通讯作者: S.Oishi