Flash vacuum thermolysis - Synthesis and characterization of unstabilized cycloalkenethiones

Article abstract of DOI:10.1002/(sici)1099-0690(199904)1999:4<869::aid-ejoc869>3.0.co;2-o

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