Cyclothiomethylation of Functional Substituted Anilines by CH2O and H2S

Abstract

N-Aryl substituted 1,3,5-dithiazinanes have been synthesized (20-60 o C) in 32-95% yield by cyclocondensation of o-, p-aminobenzoic, 4-, 5-aminosalicylic acids, p-aminobenzoic acid ethyl or (β-diethylamino)ethyl esters and p-aniline sulfamide with CH 2 O and H 2 S (1:3:2 ratio).At ambient temperature p-aminobenzoic acid, 5-aminosalicylic acid and p-aminobenzoic acid ethyl ester together with 1,3,5-dithiazinanes form appropriate N-aryl substituted 1,3-thiazetidines.Cyclothiomethylation of p-aminobenzoic acid ethyl ester (0 °C) results in N,N-diaryl-1,3,5-thiadiazinane.Heterocyclization of p-aniline sulfamide with CH 2 O and H 2 S at a molar ratio of 1:6:4 (pH 1.3-1.5)was found to afford bis-1,3,5-dithiazinanes involving two amino groups.Condensation of p-aniline sulfacetamide with 37% formalin (CH 2 O) and H 2 S (pH 2.5) led to the compound, which was built as macroheterocycle from two fragments of p-aniline sulfacetamide molecule bound to each other by sym-dimethyl sulfide chain (CH 2 SCH 2 ).