Synthesis and Spectroscopic Characterization of Selected Phenothiazines and Phenazines Rationalized Based on DFT Calculation.

Two unique structures were isolated from the phosphorylation reaction of 10-phenothiazine. The 5,5-dimethyl-2-(10-phenothiazin-10-yl)-1,3,2-dioxaphosphinane 2-oxide () illustrates the product of -phosphorylation of phenothiazine. Moreover, a potential product of instability, a thiophosphoric acid , was successfully isolated and structurally characterized. Molecule , similarly to sulfoxide derivative , possesses interesting phosphorescence properties due to the presence of d-pπ bonds. The X-ray, NMR, and DFT computational studies indicate that compound exhibits an anomeric effect. Additionally, the syntheses of selected symmetrical and unsymmetrical pyridine-embedded phenazines were elaborated. To compare the influence of phosphorus and sulfur atoms on the structural characteristics of 10-phenothiazine derivatives, the high-quality crystals of (4a,12a-dihydro-12-benzo[5,6][1,4]thiazino[2,3-]quinoxalin-12-yl)(phenyl)methanone () and selected phenazines 5,12-diisopropyl-3,10-dimethyldipyrido[3,2-:3',2'-]phenazine () and 5-isopropyl-,3-trimethylpyrido[3,2-]phenazin-10-amine () were obtained. The structures of molecules , , 2-mercapto-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (), 3,7-dinitro-10-phenothiazine 5-oxide (), and were determined by single-crystal X-ray diffraction measurements.