Sodium ethanethiolate reacts at the S-2 position of substituted 1, 2-dithiole-3-thiones to give various products depending on the substiuents at the C-4 and C-5 positions. In particular, the presence of a pyrimidinyl substituent induces some noticeable changes in the reaction pathway, yielding a novel heterocycle whose synthesis has not been previously reported.