Sulphamoyl halides

The synthesis of esters of sulphamic acids is generally achieved by the reaction of the corresponding sulphamoyl halides with an alkoxide or alcohol according to equation 20. A large variety of such esters have been prepared and the synthetic procedures and their properties have been reviewed1. The present work describes the synthetic procedures which have been developed since 1980 to incorporate the sulphamoyl ester moiety (NS03R) into molecules and to look at the general reactivity of sulphamate esters. 

Dialkylsulphamoyl (264) and monoalkylsulphamoyl (265) halides have been prepared by the reaction of amines or amine hydrochlorides with sulphuryl chloride (equation 80)264-269. Sulphuryl chloride also reacts with dialkylsulphamides to give sulphamoyl halides 266 (equation 81)270. 

N-Sulphonylamines generated from sulphamoyl halides at — 78 °C using triethylamine were also allowed to react with diazoalkanes 296. Working the reaction mixture below — 30 °C led to the isolation of 2,3-di-tm-alkylthiaziridine-l, 1-dioxides 297301. The compounds were characterised by the IR, UV, 1H-NMR spectra as well as by their quantitative decomposition into sulphur dioxide and aldimines (equation 94). 

Gilmore and Morton302 have described the first direct sulphamoylation of ester enolate anions (298). The reaction involved the addition of the t-butyl iV-sulphonylamine generated at —78 °C from the sulphamoyl halide followed by addition of the carbanion, and the solution was worked up to room temperature to yield ethyl a-(iV-t-butyl-sulphamoyl)phenyl acetate 299 (equation 95). 

Diphenyl ether sulphamides of the type 356 were prepared by the reaction of the alcohols 357 (R = H, halogen, alkyl, N02, CF3 R1 = F, Cl) with chlorosulphonyl isocyanate359. The intermediate sulphamoyl halide 358 was then reacted with amines to... 

The reaction of sulphamoyl halides with amines is a useful synthetic route to the preparation of sulphamides. Unterhalt and Seebach364 have used this approach to prepare N,N,AT-trialkylsulphamides 345 (equation 116). The reaction was carried out at 50 °C in... 

Alkyl-2-chloro- and -2-fluoro-sulphonylcarbamoyl chlorides (376), prepared simply from sulphamoyl halides RNHSO2X and phosgene in pyridine/ are useful precursors for the synthesis of 1,2,4,6-thiatriazine 1,1-dioxides, e.g. (377) and (378) (Scheme 85). ... 

III. SULPHAMOYL AZIDES, ESTERS AND HALIDES A. Sulphamoyl Azides... 

The value of ACj> of — 76 cal deg mol for hydrolysis of dimethyl-sulphamoyl chloride (21) in aqueous solution indicates a degree of solvent reorganization during transition-state formation that is similar to that involved in the SnI hydrolysis of tertiary halides. For organic solvolyses, ACp = ca. 

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