Cyclothiomethylation of primary amines with formaldehyde and hydrogen sulfide to nitrogen- and sulfur-containing heterocycles (review)

Abstract

Published data and the authors' own experimental results on the synthesis of nitrogen-and sulfurcontaining heterocycles based on the cyclothiomethylation of amines with formaldehyde and H 2 S are reviewed. Features of the three-component condensation are discussed in relation to the nature and structure of the initial amines and also the reaction conditions.

New dithiazinanes and bis‐dithiazinanes‐bearing pendant ethylamines: Structure and reactivity

“…The reactions of N-methyl-ethylene-diamine (2) and N-ethyl-ethylene-diamine (3) with formaldehyde and NaSH are complex because they give different products depending on the ratio of reagents and reaction conditions. This complex behavior is due to the presence of a secondary amine bearing a reactive proton, which promotes cyclization and substitution reactions.…”

“…The chemistry of saturated heterocyclohexanes has not been widely developed [1,2], compared to the heterocyclic chemistry of unsaturated systems. It is a consequence of their difficult synthesis and purification and to their high reactivity.…”

“…As part of our research program on heterocyclohexanes, we are investigating the structure and reactivity of new dithiazinanes [3][4][5][6] bound through chains [7] or having pendant basic groups as ethanol [8], which have found application as ligands for metal compounds of group 13 [9,10] or as building blocks for tripodal compounds [11] Herein, we report the synthesis of a new group of dithiazinanes, bearing an ethylamine attached to the endocyclic nitrogen, (compounds 4-6, Scheme 1; 7-10, Schemes 2 and 3; 11-14, Scheme 4; and 15 and 16, Scheme 5). Compounds 4-16 were synthesized from N,N-dimethyl-ethylene-diamine (1), N-methylethylene-diamine (2), and N-ethyl-ethylene-diamine (3). The ethylenediamine group of the new compounds showed a remarkable basic behavior toward methylene chloride used as solvent.…”

Effective synthesis of N-substituted 1,3,5-dithiazinanes by reactions of N-methyl-1,3,5-dithiazinane and 1,3,5-trithiane with aromatic amines

“…This reaction was studied in detail with the use of various aliphatic and aromatic amines [8]. Its considerable disadvantage is the necessity of using gaseous hydrogen sulfide and aqueous formaldehyde.…”

“…For example, the condensation of o-phenylenediamine with H 2 S-CH 2 O (Scheme 1) gives a mixture of compounds I-IV which are difficult to separate [9]. Analogous reaction with m-phenylenediamine gives rise to a mixture of various macroheterocyclic compounds, whereas p-phenylenediamine failed to react with H 2 S-CH 2 O under similar conditions [8].…”