D. Desilets et al., DESIGN AND SYNTHESIS OF NEAR-INFRARED ABSORBING PIGMENTS .2. STRUCTURE DETERMINATION OF ACEANTHRENE GREEN AND DERIVATIVES, Canadian journal of chemistry, 73(3), 1995, pp. 325-335
The reported structure of aceanthrene green, a pigment prepared by pot
assium hydroxide fusion of 1,9-anthracenedicarboxylic imide, was found
to be incorrect. The structure of the pigment is reassigned to 7,8,15
,16-dibenzo[a,j]perylenetetracarboxylic diimide on the basis of COSY,
NOESY, and inversion-recovery H-1 NMR experiments. N-Alkyl- or N-pheny
l-1,9-anthracenedicarboxylic imides, aceanthryleno[1,2-b]quinoxaline,
and a benzimidazole derivative of 1,9-anthracenedicarboxylic anhydride
were found to give the same dibenzo[a,j]perylene structure when react
ed in potassium hydroxide. The electronic spectra of these derivatives
is reported and it is shown that, as predicted by Pariser-Parr-Pople
calculations, they absorb in the near-infrared. Finally, a mechanistic
outline for the fusion is proposed on the basis of AM1 and frontier m
olecular orbital calculations.