ZfN: Search Results

1	Author	Hans-Ulrich Höfs, Rüdiger Mews, Mathias Noltemeyer, GeorgeM. Sheldrick, Martin Schmidt, Gerald Henkel, Bernt Krebs	Requires 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
	Similar Items	Find
	DEBUG INFO
	TEI-XML for	default:Reihe_B/38/ZNB-1983-38b-0454.pdf
	Identifier	ZNB-1983-38b-0454
	Volume	38

2	Author	Herbert Binder, Jürgen Palmtag	Requires cookie*
	Title	Synthesen und Reaktionen von 4-Bora-2.6-diphospha-1.3.5-triazenen Cyclische Borbetaine Synthesis and Reactions of 4-Bora-2,6-diphospha-l,3,5-triazenes Cyclic Boron Betaines
	Abstract	By substitution of chlorine in the title compound 2,2,4,4,6,6-hexachloro-3,5-dimethyl-4-bora-2,6-diphospha-l,3,5-triazene (1) new members of this class of compounds are synthesized. In most cases reaction starts first on the boron site. The ring reactivity can be accounted for in terms of the charge distribution in the heterocycle 1. In 1 the coupling 2 J(31 P-N-n B) could be detected for the first time. A mechanism for the ring formation is discussed.
	Reference	Z. Naturforsch. 34b, 179—187 (1979); eingegangen am 15. Juni/4. Oktober 1978
	Published	1979
	Keywords	Ring Reactivity, Substitution Reactions, 4-Bora-2, 6-diphospha-l, 3, 5-triazenes
	Similar Items	Find
	DEBUG INFO
	TEI-XML for	default:Reihe_B/34/ZNB-1979-34b-0179.pdf
	Identifier	ZNB-1979-34b-0179
	Volume	34