A novel and successful application of ring-closing reactions of aminophenols has been proposed for the formation of a new type of 1,3-benzoxazine ionic derivatives. The optimization of the reaction and detailed computational studies have been reported for the estimation of heterocyclic ring stability and its further transformation, which is crucial in the polymerization process. The molecular structure of the obtained compounds has been fully characterized by applying X-ray analysis and spectroscopic methods. The novel benzoxazines undergo an intriguing thermal reaction leading to classical benzoxazines and chloroalkanes, which is the first step of transformation before polymerization. To gain more insights into the transformation behavior of ionic benzoxazine derivatives, the Fourier transform infrared (FT-IR) spectra of gaseous products were recorded in experiments with near simultaneous FT-IR/TGA measurements. The combination of thermogravimetry with FT-IR spectroscopy enables the quantitative and qualitative characterization of thermal transformation products and clarification of the reaction mechanism. The experimental data have been verified by applying DFT(B3LYP) and DFT(M062x) theoretical studies.

A unique method of bisphenol/bisnaphthol synthesis is being proposed, serendipitously discovered in the course of the careful analysis of an aminophenol methylation reaction. The insightful exploration of the synthesis of N- or O-methylated species, originating from functionalized phenols obtained by a conventional strategy, provided the opportunity to discover an unexpected reaction pathway yielding various bisphenols. Sodium complexes were found to be crucial intermediates in the synthetic scenario. Their formation, which is usually an imperceptive step, was substantial for the productive outcome of functional group protection. Thorough exploration revealed an essential structural motif of aminophenolate, necessary for the successful outcome of the reaction, and also enabled establishing the limitations of the new method. The work demonstrated that a slight change in the perspective and close inspection of the synthetic nuances can answer the important question concerning what a specific target-oriented synthesis strategy is lacking.

Novel sodium coordination compounds with aminonaphtholate and aminophenolate ligands have been synthesized and characterized by spectroscopic methods, X-ray analysis, and DFT calculations. The flexible ligands framework forms tetra or binuclear...