Sulphur Di-imides

Sulphur Di-imides.—Preparation and Properties of SN). This and related sulphur-nitrogen compounds have created interest both in their preparation and their physical properties (see Vol. 5, p. 103). Pyrolysis of S4N4 gives either (SN) or depending on the reaction conditions. - The physical and spectroscopic 

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Figure 22 The proposed structure of bis(NN -methylsilanetriyl)tris(sulphur di-imide)...

The preparation of new sulphur-nitrogen compounds by the reaction of bis-(trimethylsilyl)sulphur di-imide (21) has been described.97 N-Chloro-N -tri-methylsilyl-sulphur di-imide (22) was prepared by the reaction of (21) with chlorine. 

C. The compound formed from PFs and the sulphur di-imide (62), previously thought to be a quinquecovalent phosphorane, has been shown to be the iminophosphorane (63). 

Synthesis of Isothiazoles, Isothiazolines, and Isothiazolidines 151 From amidoketones and hydrogen sulphide (Type A C-C-C-N + S) 151 From iminonitriles and mercaptoacetic acid derivatives (Type B C-C-N + S-C) 151 From cyclisation of enaminothiones (Type C N-C-C-C-S) 152 From sulphonamidoacetates and diethyl oxalate (N-S-C + C-C) 152 From ketenes and sulphur di-imides (N-S-C + C-C) 152 Physical Properties of Isothiazoles and Isothiazolines 152 Chemical Properties of Isothiazoles, Isothiazolines, and Isothiazolidines 153... 

The reaction between iVAr -bis(trimethylsilyl)sulphur di-imide and phosphorus pentafluoride gives a small amount of SaNgPFg, for which (77) is the suggested structure the n.m.r. spectrum shows two doublets,supporting... 

The synthesis of the first oxide of the S4N4 ring has been described. AW -Bis(trimethylsilyl)sulphur di-imide reacts with the anhydride of fluoro-sulphuric acid with cleavage of trimethylfluorosilane and trimethylsilyl fluorosulphate to give S4N4O4 (32). The compound is a yellow solid which... 

A new and general route to bis(trifluoromethyl)keteniniines has been provided by the discovery of a facile reaction between bis(trifluoromethyl)-thioketen and sulphur di-imides ... 

Diphenyl sulphur di-imide (338) and diphenylketen react to give a 1 2 adduct at 6-8 viz, the thiadiazepine (339), W the compound is unstable and decomposes on warming to form the 1 1 adduct (340) plus diphenyl-keten. In an interesting one-pot reaction, cyclic iViV -disubstituted... 

New metal—R insertion complexes between [( / -CjH5)Fe(CO)2Rl (R = alkyl or aryl) and (1) or sulphur di-imides have been reported. TTie photolysis of JV-phenyl-JV -sulphinylhydrazine in aromatic solvents generates phenyl radicals these undergo addition to the solvents, affording biphenyls. ... 

Preparation of Other Sulphur Di-imides. Pyrolysis of A-sulphinylaniline has been found to give sulphur di-imides in the presence of a nickel(o) catalyst. Sulphur di-imides that have the general structure RN=S=NR (R = Me3Si, MejSn, or CgF,)... 

The thiochromanones (95 R = Me or Ph) react with hydroxylamine 0-mesitylenesulphonate to yield sulphilimines (96) these, with base, rearrange to 1,2-benzisothiazoles (97). A remarkable preparation of a 1,2-benzisothiazole (99 X = S) and of a 1,2-benzisoselenazole (99 X = Se), by the reaction of 2,l,3-benzothia-(or selena-)diazole (98 X = S or Se) with benzyne, has been reported. Another interesting synthesis, this time of a 2,1-benzisothiazole (102), is by the reaction of the fluorosilylated amine derivative (100) with bis(tri-methylsilyl)sulphur di-imide (101). ... 

Synthesis.—Another report has appeared of the condensation of sulphur di-imides ArN=S=NAr with oxalyl chloride to give, in this case, 2,5-diaryl-l-arylimino-1,2,5-thiadiazolidine-3,4-diones (174). 3-Chloro-4,4-dimethyl-A -1,2,5-thiadiazoline 5-oxide (175) and the dioxide (176) arise in good yield from the interaction of 2-amino-2-cyanopropane with thionyl or sulphuryl chloride, respectively. The halogen is replaced by basic groups. ... 

Sulphimides.—(S)-(-)-2-Carboxyphenyl methyl N-toluene-p-sulphonyl sul-phimide (68 2-carboxyphenyl in place of Tol) may be prepared by the reaction of the corresponding sulphide with Chloramine-T, foUowed by conventional resolution, or from the optically active sulphoxide by reaction with NN -bis(toluene-p-sulphonyl)sulphur di-imide. " Acid-catalysed hydrolysis gives the sulphoxide with retention of configuration, and an-chimeric assistance by carboxylate is demonstrated, as for reactions of the sulphoxide itself. " (R)-(+)-Methyl-p-tolyl sulphoxide reacts with tol-uene-p-sulphonyl isocyanate to give the corresponding N-toluene-p-sulphonyl sulphimide (68) with net inversion, though product and recovered sulphoxide are partly racemized. The same sulphoxide reacts with toluene-... 

Thiazetidines and Thiazetes.— The reaction of sulphur di-imides with ketens leads ultimately to 1,2-thiazetidine derivatives (1 by way of intermediates (185) and (186). Oxidation of (187) with m-chloroperbenzoic acid leads to the S-oxide (188). The 1,2-thiazetidine intermediate proposed to account... 

The synthesis of 1,2,5-thiadiazoles from sulphur di-imides andketens (these Reports, Vol. 1, p. 453, Vol. 2, p. 752) has been more closely studied. The course of the cycloaddition is temperature-dependent, resulting in the labile... 

SS-Disubstituted sulphur di-imides (219) are attracting increasing attention as synthetic reagents. Their interaction, in dilute solution, with the difunctional oxalyl chloride, in the presence of triethylamine, affords the substituted l,2,5-thiadiazole-3,5-diones (220) almost quantitatively. ... 

Various thiazine 1-oxides (S) and 1-N-imines (6) have also been obtained by cycloaddition of 2,3-dimethylbutadiene to the appropriate N-sulphinyl-amides and symmetrical sulphur di-imides, respectively. 

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