250690-36-9Relevant articles and documents
Synthesis of highly functionalized pyrazines by ortho-lithiation reactions. Pyrazine ladder polymers
Zhang, Carol Y.,Tour, James M.
, p. 8783 - 8790 (2007/10/03)
Several novel transformations on sensitive pyrazine cores are disclosed while preparing monomers for condensation polymerizations to planar polypyrazines. Two pyrazine monomers for the step growth polymerization are prepared starting from ethyl acetoacetate and proceeding via pyrazine-2,5-dicarboxylic acid as the common intermediate. The dicarboxylic acid serves as the key intermediate for the preparation of both the A and B components for the step-growth polymerization. A bis(Curtius) rearrangement followed by tert-butyl alcohol capture of the diisocyanate effects the high-yielding conversion of carbonyl moieties to the tert-butoxycarbonyl-protected aryldiamine. Since electrophilic halogenation of the pyrazine nucleus was unsuccessful due to the inherent electron deficiency of pyrazines, a directed ortho-metalation is disclosed using tert-butoxycarbonyl-protected amines and neopentyl glycol acetals as the metalation directing groups. Pd/Cu-catalyzed couplings of diiodopyrazines with distannylpyrazines are utilized for the polymerization schemes. This approach permits the ladder linkages of the planar polymers to (i) form in high yields upon ZnCl2 activation once the polymer backbone is intact, (ii) be substituted so that the newly formed polypyrazines are soluble, unlike many other aromatic ladder polymers, and (iii) contain double-bonded ladder units to keep the consecutive aryl moieties planar which maximizes extended π-conjugation through the polymer backbones, thereby increasing the bandwidths and lowering the optical band gaps.
