1 research outputs found
Ru-Catalyzed Polycondensation of Dialkyl 1,4-Phenylenebis(diazoacetate) with Dianiline: Synthesis of Well-Defined Aromatic Polyamines Bearing an Alkoxycarbonyl Group at the Adjacent Carbon of Each Nitrogen in the Main Chain Framework
Transition-metal-catalyzed
N–H insertion of a diazocarbonyl
compound is applied for polycondensation for the first time to give
a new type of aromatic polyamine. The well-defined polyamines were
obtained by [RuCl<sub>2</sub>(<i>p</i>-cymene)]<sub>2</sub>-catalyzed reaction of diethyl 1,4-phenylenebisÂ(diazoacetate) with
dianilines bearing a variety of linkers between two aniline units.
The polycondensation proceeded at 30 °C in CH<sub>2</sub>Cl<sub>2</sub> with 5.0 mol % of the Ru metal to [NH<sub>2</sub> or N<sub>2</sub>C] to afford the products with <i>M</i><sub>n</sub> = 6400–28 300 in moderate to high yield. Ethoxycarbonyl
groups located at an adjacent position to NH imparted solubility to
the polyamines, and their glass transition temperatures can be varied
depending on the linker structure in a range of 88–173 °C