Soluble oligoaramide precursors--a novel class of building blocks for rod-coil architectures

A new synthetic route is described that allows the reversible conversion of the inherently insoluble oligo-p-benzamides into soluble materials through the formation of imidoyl chlorides. Syntheses of the corresponding dimer, trimer, and tetramer are reported; these compounds can easily be purified by crystallization and are accessible on the multigram scale. Structural proof was obtained by single-crystal X-ray structures of the trimer and tetramer precursors. They can be selectively functionalized into amides or esters at the terminal carboxylic acid group followed by hydrolysis of the imidoyl chlorides to the parent amides. This new class of compounds gives access to strongly aggregating rigid rodlike materials in few synthetic steps, as is demonstrated by the preparation of poly(ethylene glycol)-co-oligo(p-benzamide) rod-coil block copolymers.