4H-3λ2-Thieno[3,2-d]pyrimidin-4-one derivatives are of interest as biologically active compounds. In this communication, 2-(chloromethyl)-4H-3λ2-thieno[3,2-d]pyrimidin-4-one (1) was investigated in the reaction with ammonia, potassium phthalimide, and other basic agents. The dimerization product—8,18-dithia-1,4,11,14-tetrazapentacyclo[11.7.0.03,11.05,9.015,19]icosa-3,5(9),6,13,15(19),16-hexaene-10,20-dione was formed in the reaction with potassium phthalimide in DMF, by heating at 110 °C for 5 h. The structure of the newly synthesized compound was established by means of elemental analysis, high resolution mass-spectrometry, 1H, 13C NMR, and IR spectroscopy, and mass-spectrometry.