Ergebnisse aus versuchen zur darstellung von bis(trifluormethylsulphanyl)thioketen (CF3S)2C=C=S

The attempted preparation of bis(trifluoromethylsulphanyl)thioketene is described. Mono-and di-(trifluoromethylsulphanyl)-substituted orthothioesters may be prepared fromCH₃C(SC₂H₅)₃ and CF₃SCl in the presence of anhydrous ZnCl₂. The unstable compoundshave been isolated and characterized. The corresponding CF₃Se and CF₃SO₂ derivativesare only formed as intermediates which decompose to ketene diethylmercaptal. Suchmono- and di-substituted products are obtained in good yield from H₂C=C(SC₂H₅)₂ andCF₃ECl (E=S, Se). The reaction of H₂C=C(SC₂H₅)₂ with CF₃SO₂F gave only poor yieldsof (CF₃SO₂)_nCH_2?n=C(SC₂H₅)₂ (n=1, 2) which were only capable of characterizationin etheral solution by spectral means. Attempts to prepare (CF₃S)₂C=C=S by refluxing(CF₃S)₂CHC(O)Cl, (CF₃S)₂CHC(O)OH or (CF₃S)₂C=C=O with P₄S₁₀ in toluene yieldedonly the cyclic dimer and the corresponding 1,3,4-trithiolan.