The flash vacuum thermolysis (FVT) of cycloalkenyl allyl (or from cyclopentenethione 1. The obtention of the nonconjugated cycloalkenethiones 2 and 4, expected in the propargyl) sulfides 8, 9, 12, and 13 led, as the main thermal pathway, to the conjugated cycloalkenethiones 1, 3, and 5, FVT of sulfides 10 and 11, has been confirmed only by UV/ Vis spectroscopy at -196 °C, due to their rapid resulting from a retro-ene reaction. These reactive thioketones, thus obtained in ca. 70% yield, have been enethiolization. In the case of the large-ring sulfide 14, the (E) geometry of the double bond favoured the competitive characterized in the gas phase by mass spectrometry, and at low temperature by IR, UV/Vis and NMR spectroscopy. The retro-ene reaction yielding cyclododecene and propynethial; on the other hand, the FVT of the tricyclic gem-dithiol 15, a polymerization of 1, 3, and 5 upon warming is generally more rapid than the other attempted reactions and only the [2 + possible precursor of cyclobutenethione ( 7), led to vinyl thioketene (18), obtained by thermal ring opening of 7. 3] dipolar cycloaddition with diazomethane led in low yield, besides polymeric materials, to isomeric 1,3-dithiolanes 20