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'N Sulphenylchlorides' in keywords Facet   section ZfN Section B  [X]
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1983 (1)
1Author    Hans-Ulrich Höfs, Rüdiger Mews, Mathias Noltemeyer, GeorgeM. Sheldrick, Martin Schmidt, Gerald Henkel, Bernt KrebsRequires cookie*
 Title    Reactions of Fluorinated Nitriles with Sulphur(II) Chlorides; Crystal Structure of 2,4,6-Tris(difluorosulphoximido)-l,3,5-triazene at 170 K  
 Abstract    The addition of CF3SC1 (2) to the fluorinated nitriles RfCN[Rf = CF3 (3), NSF2 (4), NSOF2 (5)] leads to N-perfluoromethanesulphenyl-formylimidoylchlorides CF3S-N = C(C1)/?/ (6, 11, 12). From the reactions of SC12 (1) with (3) and (5), which yielded the N-sulphenyl-chlorides C1S-N = C(C1)-R/ (7, 13), it proved possible also to isolate the oxidation product [CF3CC12NSC12 (8)] and an oligomer of the nitrile [(NCNSOF2)3 (14)]. Dechlorination of 7 with Hg gives the corresponding di-and tri-sulphides (CF3C(Cl) = N-)2Sa; (9, 10, x — 2, 3). Crystals of (14) are triclinic with a = 1133.6(5), b = 1332.6(5), c = 1715.1(8) pm, a = 109.31(3), ß = 105.30(3), y = 97.84(3)° at 170 K, Z = 8, space group P I. The structure was refined to R = 0.028 for 8290 diffractometer data with F > 4cr(F). The four crystallo-graphically independent molecules adopt similar unsymmetrical conformations. N-Sulphenylacetimidoyl halides of the type RC(X)=N-S-Y are important in preparative chem-istry for several reasons: (a) When Y is a halogen, it may be readily exchanged, leading to a chemistry analogous to that of the perhaloalkylsulfenylhalides RhaiSCl [1, 2]. Examples of such substitution reac-tions have already been reported [2, 3], (b) When the substituent X on the triply-coordinated carbon is a halogen, the -M effect of the imino-nitrogen facilitates nucleophilic attack. Hard nucleophiles (fluoride, alcohols, amines) tend to replace X [4], soft nucleophiles the sulphur-substituent Y. (c) The >C=N-S-system may be regarded as a shortened diene, in which the second double bond is replaced by the oxidisable sulphur atom; instead of the usual 1,4-addition this results in 1,3-addition with simul-taneous oxidation of the sulphur [5]. One of the simplest examples of this class of com-pounds , chlorosulphenylchloroformylimidoylchloride may be prepared in several ways; the synthesis [6] from C1CN and SC12 opens a general route to the N-sulphenylimidoyl derivatives [4, 7-9]: C1CN + SC12 C1S-N=CC12 1 RCN + R'SCl -> R'S-N=CC1R 2 * Reprint requests to Prof. R. Mews. 0340-5087/83/0400-0454/$ 01.00/0 We report here an investigation of the corresponding addition of CF3SCI and SC12 to the fluorinated nitriles N = C-CF3, N = C-NSF2 and N = C-NSOF2. Experimental 
  Reference    Z. Naturforsch. 38b, 454—459 (1983); eingegangen am 8. November 1982 
  Published    1983 
  Keywords    Crystal Structure, Perfluoromethanesulphenylformylimidoylchlorides, N-Sulphenylchlorides, 1, 3, 5 -Triazenes 
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 Identifier    ZNB-1983-38b-0454 
 Volume    38