title: Acylthioketene-thioacylketene-thiet-2-one rearrangements
abstract: Flash vacuum thermolysis (FVT) of 6-aryl-1,3-dioxine-4-thiones 9 leads to the formation of acylthioketenes 10, which are characterized by Ar matrix IR spectroscopy as well as on-line tandem mass spectrometry. The thioketenes 10 undergo a 1,3-shift of the aryl group to generate thioacylketenes 11. Ketenes 11 cyclize to 3-aryl-thiet-2-ones 12, which are also characterized by matrix IR spectroscopy and tandem mass spectrometry. The thiet-2-ones 12 undergo two kinds of reaction under the FVT conditions: (i) cheletropic CO extrusion with formation of arylthioketenes 13, and (ii) cycloreversion to COS and arylacetylene.
authors.affiliation: Chemistry Department, University of Queensland, Brisbane, Australia.
authors.initials: JR
authors.lastname: Ammann
authors.initials: R
authors.lastname: Flammang
authors.initials: MW
authors.lastname: Wong
authors.initials: C
authors.lastname: Wentrup