Aminomethylation of hydroxyacetonafton primary and secondary amines with excess of formaldehyde has been carried out. It revealed that the use of secondary amines 1-hydroxy-2- and 1-hydroxy-4-acetonaftone makes it possible to obtain directly the aminomethyl derivatives, and while amines 1-hydroxy-2-acetonaftones do not expose to the Mannich reaction with primary aromatic amines, 1-hydroxy-4-acetonaftones with primary aromatic amines which accounted for 3,4-dihydro-3-aril-6-aceto-2H- benzoxazines. Composition and structure of the synthesized connections established on the basis of data of the element analysis and PMR-spectral have been identified.