Matsumoto, T. Simple One–Pot Synthesis of Hexakis(2-alkoxy-1,5-phenyleneimine) Macrocycles by Precipitation–Driven Cyclization. Macromol2024, 4, 1-22.
Matsumoto, T. Simple One–Pot Synthesis of Hexakis(2-alkoxy-1,5-phenyleneimine) Macrocycles by Precipitation–Driven Cyclization. Macromol 2024, 4, 1-22.
Matsumoto, T. Simple One–Pot Synthesis of Hexakis(2-alkoxy-1,5-phenyleneimine) Macrocycles by Precipitation–Driven Cyclization. Macromol2024, 4, 1-22.
Matsumoto, T. Simple One–Pot Synthesis of Hexakis(2-alkoxy-1,5-phenyleneimine) Macrocycles by Precipitation–Driven Cyclization. Macromol 2024, 4, 1-22.
Abstract
Hexakis(2-alkoxy-1,5-phenyleneimine) macrocycles were synthesized using a simple one−pot procedure through by precipitation−driven cyclization. The acetal−protected AB−type monomers, 2-alkoxy-5-aminobenzaldehyde diethyl acetals, underwent polycondensation in water or acid−containing tetrahydrofuran. The precipitation−driven cyclization based on imine dynamic covalent chemistry and π−stacked columnar aggregation played a decisive role in the one−pot synthesis. The progress of the reaction was analyzed by MALDI−TOF mass spectrometry. The macrocycles with alkoxy chains were soluble in specific organic solvents such as chloroform, allowing their structures to be analyzed by NMR. The shape−anisotropic, nearly planar, and persistent macrocycles aggregated into columnar assemblies in polymerization solvents, driven by aromatic π−stacking. The octyloxylated macrocycle OcO−Cm6 exhibited an enantiotropic columnar liquid crystal−like mesophase between 165°C and 197°C. In the SEM image of (S)-(−)-3,7-dimethyloctyloxylated macrocycle (−)BCO-Cm6, columnar substances with a diameter of 100−200 nm were observed. The polymerization solution for 2-(2-methoxyethoxy)ethoxy)ethoxylated macrocycle (TEGO−Cm6) gelled and showed thixotropic properties by forming a hydrogen bond network.
Chemistry and Materials Science, Applied Chemistry
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