Sulfimides, cyclic

Moody and co-workers independently reported the synthesis of azathiabenzenes by thermolysis <86JCS(P1)483>. Azides 51a and 51b were decomposed in boiling toluene to give the corresponding cyclic sulfimides 52a and 52b in 52% and 13% yields, respectively (Scheme 14). 

The steric effects and rate constants for the reaction of cyclic sulfides, such as thietane with chloramine I (H3CC6H4NCl"Na ), in which the sulfides are converted to sulfimides and sulfoxides, have been investigated. ... 

Treatment of iV-(2-phenylthio)phenylbenzamidine with /V-chlorosuccinimide (NCS) leads to the cyclic sulfimide (499) (78CC1049). 

Compounds containing an ylidic N—S bond are best considered as cyclic sulfimides, and as such can be prepared by methods used for their acyclic counterparts (77CRV409). For example, oxidative ring closure of (181) with bromine gives the cyclic sulfimide (93) (64LA(675)189), and treatment of JV-(2-phenylthio)phenylbenzamidine with N-chlorosuc-cinimide (NCS) leads to the cyclic sulfimide (182) (78CC1049). 

Dithiazoles investigated are given in Figure 1(a) these are 1,2,3-dithiazolium cations 1, 1,2,3-dithiazolyl radicals 2, l,2,3-dithiazole-3-ones 3 and related compounds 4, their 2-oxides 5. 1,2,3-Oxathiazoles have been obtained and investigated in the form of their A-oxides (Figure 1(b) and named as cyclic sulfamidates 7 and 8 and sulfimidates 6, 9, and 10. 

Cyclic sulfimidates can be easily oxidized to the corresponding sulfamidates. The preparation of sulfamidates from tvV-aminoalcohols can be achieved in one step without isolation of intermediate mono-A-oxides (Equation 37) <20010L405, 2002TL1915, 2005TA1583>. Yields are from moderate to high. 

The traditional synthesis of cyclic sulfimidates from /3-aminoalcohols and SOCl2 in the presence of amine as a base has been developed further to the preparation of the enantiopure monocyclic as well fused sulfimidates (Schemes 26 and 27). 1,2,3-Oxathiazolidine mono-.Y-oxides are readily oxidized to corresponding sulfamidates by RuCR and NalCb, and the synthesis of sulfamidates can be performed in a one-pot procedure from -aminoalcohols without isolation of intermediate sulfimidates (Equation 37). The reaction of sulfamate esters 145 with PhI(OAc)2 and various catalysts proved to be a reliable method for the enantioselective preparation of cyclic sulfamidates 146 (Equation 35). 

Imidation and 3 -methylation were also investigated. Hoping to obtain five-membered cyclic sulfimide 37, imida-tion was carried in methylene chloride but afforded only silanol 38 as the major product. Finally, sulfonium salt 39 was prepared by treatment of sulfide 32 with methyl iodide in dry ethanol, and was found to be fairly stable under dry conditions. 

The nitrene generated by thermolysis of 3-azidothiophene can also be captured by a suitably positioned divalent sulfur to form an S,N-ylide <86JCS(P1)483>. 2-Azathiabenzenes (519) fused to the thiophene ring have been prepared in this manner (Scheme 110). The 3,4-disubstituted thiophene (520) gave an unstable cyclic sulfimide (521). Cyclic suliimides in which the positions of the sulfur and nitrogen atoms are reversed with respect to the thiophene ring could also be made by this procedure. 

Imides s. Dicarboxylic acid imides, Sulfimides Imidines s. Phthalimidines Imidine-type compounds, cyclic s. Naphthyridines, 2,7-diiminooctahydro-N-Imidoylethylenimines... 

Ring opening of cyclic sulfimidic acid esters... 

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