SYNTHESIS AND STRUCTURE OF HETEROCYCLIC QUINONE ARYLAMINES AS MODEL COMPOUNDS FOR POLYAROMATIC QUINONE IMINES

The structures of model compounds for the polyaromatic quinone diimine polymers were determined. These polymers were obtained by polycondens ation of tricyclic quinones with aromatic diamines in the presence of titanium tetrachloride and 1,4-diazabicyclo[2.2.2]octane. The N-phenyl diimine and monoimine derivatives of the following quinones were synth esized: naphthoquinone, 2-methyl- and 2-tert-butyloxazolonaphthoquinon e, 2,2'-dimethylbis(oxazolo)benzoquinone, and bisthiophenobenzoquinone . X-ray single-crystal structure determinations are reported for the f ollowing derivatives: N,N'-bis(p-fluorophenyl)naphthoquinone henyl-2-t ert-butylnaphthol[2,3-d]oxazole-4,9-dione 4-imine and 9-imine, orophen yl)-2-tert-butylnaphtho[2,3-d]oxazole-9-one 4-imine, N-phenyl-2-isobut ylnaphtho[2,3-d]oxazole-9-one 4-imine, and '-diphenylbenzo[1,2-b:4,5-b ']dithiophene-4,8-dione diimine. The following common features are obs erved for these structures: the central ring systems are planar in con trast to the anthraquinone diimine derivatives in which the central ri ng system is buckled, the N-phenyl ring is twisted out of the plane of the central ring system, and the N-phenyl rings are twisted toward th e ring with the heteroatom and away from the C-H group on the adjacent ring. Molecular modeling calculations are found to be in agreement wi th the X-ray structures. The implications of the crystal structures of the model compounds for the polymeric structures are discussed.