3+3] HeterocyclizationsAlthough the formation of 2-thioxo-or 2-mercaptopyrimidine system using [3+3] heterocyclization process has been less explored there are some published examples in literature. Thus, Miyamoto's 24 group had investigated the interaction of 2-(ethoxymethylidene)malononitrile (2) with methyl N'-cycloalkylylidenecarbamohydrazonothioates 1, which led to the formation of spirocondensed heterocyclic systems 3 containing pyrimidine ring (Scheme 1).The known methods for synthesis of thioxopyrimidines and their condensed analogs with exocyclic sulfur atom are summarized and discussed. The most popular approaches are based on [3+3], [4+2], [5+1] cyclization processes or domino reactions. The literature data analysis shows that the title compounds possess diverse biological activities, such as antioxidant, radioprotective, analgesic, antiinflammatory, antihypertensive, anxiolytic, anamnestic, anticonvulsant, antimicrobial, fungicidal, herbicidal, antiviral, and anticancer.