Experimental and Computational Study of Novel Pyrazole Azo Dyes as Colored Materials for Light Color Paints

This paper presents the synthesis of eight new pyrazole azo dyes using ethyl 5-amino-3-methyl-1H-pyrazole-4-carboxylate as the diazotization component and various active methylene derivatives as coupling components. These new azo dyes were characterized by spectroscopic (FT-IR, UV-VIS), and spectrometric (¹H NMR, ¹³C NMR, MS) analyses. The dye structures were modeled by the MMFF94s force field and quantum chemical density functional theory (DFT) calculations using the B3LYP functional and the 6-311G(d,p) basis set, in the gas phase. Weak electrostatic hydrogen bonds for the azo and hydrazo dye tautomers were found in the ground state. The CIS, TD (using the B3LYP and M06-2X functionals), and ZINDO methods were used to estimate the dye UV-VIS spectra in ethanol, which were compared with the experimental ones. The anti-configuration arrangement of the π-bonds and the presence of the prevalent hydrazo dye tautomer were supported by the computed ¹H NMR and ¹³C NMR spectra. A good accordance between the experimental and predicted absorption maxima and chemical shifts was observed. Color investigations using the CIEL*a*b* space were conducted for all dyes in powder and for their mixtures in water-based acrylic resins. The results confirm the newly synthesized dyes' color properties and that they might be used for light color paints in the varnishes industry.