Sulfuryl chloride reaction with ammonia

Sulfamide (136) can be prepared by reaction of sulfuryl chloride (128) with excess ammonia in dichloromethane at -50°C, followed by extraction of the product with acetonitrile (Scheme 55). By using primary amines in the condensation, the method can be extended to obtain N,N -disubstituted sulfamides (137) (Scheme 55). A valuable route to di- and trisubstituted sulfamides involves the reaction of catechol sulfate (138) with aniline. Aniline reacts slowly with (138) to give the sulfamoyl ester (139). The unreacted aniline then promotes base-catalysed elimination of catechol to form the transient, highly reactive N-phenylsulfonylimine (140) which is trapped by aniline to yield N,N -diphenylsulfamide (141). By reaction of the ester (139) with an alkylamine, the procedure can be used to obtain trisubstituted sulfamides (142) (Scheme 56). In general, the amination of the 2-hydroxyphenyl sulfamate esters using alkylamines is an efficient route for the synthesis of trialkylsulfamides (143) (Scheme 57). 

The reaction of S02(NH2)2 with sulfuryl chloride followed by the treatment with ammonia produce the ammonium salt of cyclic, chair-shaped [N3S306]3 (47a) anion.121 The selenium analogue [N3Se306]3 (47b) adopts a similar conformation. 

In 1921 Helferich [34J found that treatment of methyl a-D-glucopyranoside 18 with sulfuryl chloride in a mixture of pyridine and chloroform at 5°C afforded a compound, the structure of which was established several years later [37,38] to be that of methyl 4,6-dichloro-4,6-dideoxy-a-D-galactopyranoside 2,3-cyclic sulfate (19 Scheme 3). The cyclic sulfates are readily cleaved by dilute alkalis, or by methanolic ammonia, to give the salt of a monosulfate the hemi-ester is then desulfated by acid to yield the chlorodeoxy sugar [35,36]. Both of these reactions occur with retention of configuration [37]. 

Of the various possible types of -substituted sulfamoyl (sulfamyl) chlorides, the dialkyl compounds are of particular interest because they serve as intermediates in the syntheses of substituted sulfamides (synthesis 28) and of certain of their derivatives (synthesis 29). The dialkyIsul-famoyl chlorides have been prepared by the reaction of sulfuryl chloride with an appropriate amine or its hydrochloride, " by the treatment of secondary 7V-chloroamines with liquid sulfur dioxide, and by the reaction of dialkyl-aminosulfinic acids with chlorine in carbon tetrachloride. Although either of the first two procedures can be recommended in terms of convenience and yield, the availability of starting materials normally dictates that the first be used. It is of interest that treatment of sulfuryl chloride with either ammonia or ammonium chloride in terms of this procedure does not give the parent sulfamoyl chloride, H2NSO2CI. This compound is obtained in an altogether different way. ... 

The quantity of trimeric and tetrameric sulfimide recovered from the reaction products of NH3 with excess S03 in nitromethane did not in any way correspond with that expected from the equations given above and only 10% of the quantity of sulfimide expected was isolated. The residue which had the composition (HNS02)reH2S04 proved to be polysulfimide sulfonic acid (LXXIV) (5). This may be regarded as an imido derivative of the polysulfuric acids. Amides of these acids have already been obtained by Ephraim and Michel (30) by decomposing sulfuryl chloride with ammonia. 

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