Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines

MARTIN HAVLÍK; TEREZA NAVRÁTILOVÁ; MICHAELA DROZDOVÁ; AMENEH TATAR; P. A. LANZA CASTRONUOVO; DIEGO DUSSO; E. LAURA MOYANO; CARLOS A. CHESTA; D. MARIANO A. VERA *; BOHUMIL DOLENSKÝ

MOLECULES

MOLECULAR DIVERSITY PRESERVATION INTERNATIONAL-MDPI

Lugar: Basel; Año: 2023 vol. 28 p. 1549 - 1549

1420-3049

The reactions of 2-naphthylamine and methyl 6-amino-2-naphthoate with formalin and paraformaldehyde were studied experimentally, spectrally, and by quantum chemical calculations.It was found that neither the corresponding aminals nor imines were formed under the described conditions but could be prepared and  spectrally characterized at least in situ under modified conditions. Several of the previously undescribed intermediates and by-products were isolated or at least spectrally characterized. First principle density functional  theory (DFT) calculations were performed to shed light on the key aspects of the thermochemistry of decomposition and further condensation of the corresponding aminals and imines. The calculations also revealed that theelectrophilicity of methanal was significantly greater than that of ordinary oxo-compounds, except for perfluorinated ones. In summary, methanal  was not behaving as the simplest aldehyde but as a very electron-deficient oxo-compound.