STRUCTURE-ANALYSIS OF A COLORING AND DECOLORING UNSYMMETRICAL FLUORAN DYE BY C-13 NUCLEAR-MAGNETIC-RESONANCE METHOD

Unsymmetrical fluoran dyes whose coloring-to-decoloring reversible reaction depends upon the acidity are used in heat-sensitive recording systems. The reversible reaction corresponds to open-to-closed forms of the lactone ring. We observed remarkable chemical shift differences in 4 species of C-13 NMR signals between open- and closed-forms of the lactone ring of an unsymmetrical fluoran dye, 3-diethylamino-6-methyl-7-chlorofluoran (DEAMCF) in CDCl3. According to the optimized molecular structure of DEAMCF by a semi-empirical molecular orbital (MO) Austin Model 1 (AM 1) method, the xanthene moiety in colorless form is folded at 166 degree around the C(spiro)-O(xanthene) axis, and the benzolactone moiety is almost perpendicular to the xanthene moiety. The moiety in color form for a molar DEAMCF/H2SO4 ratio of 1/2.2 becomes almost planar and has canonical structure, while the lactone ring opens, according to NMR and MO analyses.