Umsetzungen von K2N2S mit Fluorsulfonsäure in SO2 werden 14N‐NMR‐spektroskopisch im Temperaturbereich –80 bis +20°C verfolgt. Hierbei entstehen NH 4+, SO2(NH2)2 und ein Produkt mit einem bei –149 ppm auftretenden Signal, das zuverlässig nicht identifiziert werden konnte. Mit steigender Temperatur nimmt die Konzentration an NH 4+ zu und die der anderen Produkte ab, bis schließlich bei 20°C nur noch NH 4+ vorhanden ist. Die Bildung von SO2(NH2)2 ist auf Reaktionen mit SO2 zurückzuführen; in einem anderen Lösungsmittel tritt es nicht auf. Setzt man der Fluorsulfonsäure AsF5 zu, so entstehen bei 20°C NH 4+, N2, NS 2+ und [H2N  S  NH2] ++. Bereits bei − 80°C tritt NH 4+ und [H2NSNH2]++ auf, charakterisiert durch das Auftreten eines Quintetts und Tripletts im 14N‐NMR‐Spektrum. Der Reaktionsverlauf ist von der AsF5‐Konzentration unabhängig.

ChemInform Abstract Thermal decomposition of the unstable sulfimide (I) produces the oligomers (II). The monomeric CF3SN, generated in situ by thermolysis of the azide (III), reacts with hexachlorocyclopentadiene (IV) to give the adduct (V). (Mechanism).

CF3S(Cl) = NSi(CH3)3 is found to undergo intermolecular decomposition to give oligomeric, possibly cyclic (CF3SN)x rather than monomeric CF3SN, formed by intramolecular decomposition. Monomeric thiazyltrifluoromethane, CF3SN, is formed in the thermal decomposition of CF3SN3 and may be trapped before polymerizing by formation of a 1:1 adduct with hexachlorocyclopentadiene. The structure of this adduct is determined by single crystal X-ray diffraction. From the molecular structure it is evident that a (4 + 2) cycloaddition has not occurred but rather the formation of a thioketimine (I). The same material is formed when a suspension of CF3SNH2 and lead(IV) acetate in CH2Cl2 is refluxed and the intermediate CF3SN is again trapped by C5Cl6.By comparison ClSN and C5Cl6 interact in an analogous manner to give C5Cl6NSCl (II), whose structure was determined by single crystal X-ray diffraction. FSN, on the other hand, when reacted with CsCl6 yields the corresponding fluoro derivative only as an intermediate. At 20 °C using SO2 as solvent C5Cl6NSCl (II) is formed. At 75 °C in SO2 the new compound C5Cl6N—S—NSO forms. The latter compound may also be formed from (II) and Hg(NSO)2. In the reaction of FSN with CsF6 only decomposition products were observed.Some of the reactions of C5Cl6NSCl (II) were investigated. With Hg(SCF3)2 C5Cl6N—SSCF3 is obtained; with SbCl5 in SO2 C5Cl6N—S—NC5Cl6 forms as the main product. Keywords: synthesis of CF3SN, preparation of C5Cl6NSX (X = CF3, Cl, NSO, SCF3, C5Cl6N), crystal structures of C5Cl6NSX (X = CF3, Cl), chemical properties of C5Cl6NSCl, nmr-, ir-, ms-data.

Thermal decomposition of CF3‐S(Cl)=N‐SiMe3 is found to give oligomeric, possibly cyclic (CF3‐SN)x rather than monomeric CF3‐SN.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.