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

MARTIN HAVLIK; TEREZA NAVRATILOVA; MICHAELA DROZDOVÁ; AMENEH TATAR; LANZA, PRISCILA AILÍN; DIEGO DUSSO; ELIZABETH MOYANO; CHESTA, CARLOS ALBERTO; VERA, D. MARIANO A.

MOLECULES

MOLECULAR DIVERSITY PRESERVATION INTERNATIONAL-MDPI

Año: 2023 vol. 28 p. 1 - 19

1420-3049

The reactions of 2-naphthylamine and methyl 6-amino-2-naphthoate with formalin andparaformaldehyde were studied experimentally, spectrally, and by quantum chemical calculations.It was found that neither the corresponding aminals nor imines were formed under the describedconditions 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 atleast spectrally characterized. First principle density functional theory (DFT) calculations wereperformed to shed light on the key aspects of the thermochemistry of decomposition and furthercondensation of the corresponding aminals and imines. The calculations also revealed that theelectrophilicity of methanal was significantly greater than that of ordinary oxo-compounds, exceptfor perfluorinated ones. In summary, methanal was not behaving as the simplest aldehyde but as avery electron-deficient oxo-compound.