Aminomethylation of trifunctional 2.5-dihydroxyacetophenone (2.5-DHA) and 2.4-dihydro­xy­aceto­phenone (2.4-DHA) by free primary and secondary amines in the presence of formaldehyde has been conducted for the first time. It has been established that 2.5-DHA is aminomethylated with secondary heterocyclic amines - piperidine and morpholine and with aqueous formaldehyde solution in alcohol medium at 50⁰C. The reaction proceeds simultaneously via all three functions forming stable C,O-substitution products − β-amino-2-aminomethoxy-4-aminomethyl-5-hydroxypropiophenones. The aminomethylation reaction of 2.4-DHA proceeds by phenolic function only under the action of methylene bis-amines piperidine and morpholine in absolute alcohol at 20⁰C with the formation of 2.4-dihydroxy-3-aminomethylacetophenones. Aminomethylation of 2.4-DHA with primary aromatic amines - n-to­luidine and n-anisidine proceeds in absolute alcohol under the action of formaldehyde in the form of paraform in the presence of catalytic amounts of KOH at 50⁰C. The reaction products are 3.4-dihydro-2H-1.3-benzoxazines. 2.5-DHA does not react with primary aromatic amines and formaldehyde. The composition and structure of compounds synthesized have been established according to the data of ele­mental and spectral methods of analysis

doi.org/10.32737/0005-2531-2022-3-81-86