Sulfamoyl chlorides

Acetamidothiazole and its 4-alkyl derivatives react with chloro-sulfonic acid. The structure of the resulting products was a subject of controversy (172. 393-397). N-acetyl-A -(2-thiazolyl)-sulfamoyl chlorides (189) first proposed were then shown to be 2-acetamido-5-chloro-sulfonylthiazoles (190) (Scheme 120) (367. 368. 398). the latter assignment is based on infrared (368) and chemical evidence (367). 

Sulfamoyl chloride [7778 2-9] forms from reaction with thionyl chloride (15,16) ... 

N (C6Hi0)SO2C1 Pentamethylene-sulfamoyl chloride, 8 110 N(C8H,0)SO2(NC4H8O) N,N-Pentamethylene-4-morpho-linesulfonamide, 8 113 (NC6Hio)2S02 N,N,N, N -Di-... 

Sulfonyl imides (78) are, like sulfenes, prepared by dehydrohalogenation of the corresponding sulfonyl chlorides (79) (usually called sulfamoyl chlorides). Like sulfenes, they take part in [2 + 2] and [4 + 2] cycloaddition reactions with electron-rich alkenes or with 1,3-dienes, yielding 1,2-thia-zetidine 1,1-dioxides (80)104 or dihydro-1,2-thiazines (81),105 respectively. 

As mentioned in the introduction, recent synthetic developments now allow access to the 1,2-thiazine structure via disconnection type C (Figure 23). This process can be accomplished by a Friedel-Crafts-type cyclization of sulfamoyl chlorides. The initial report of this reaction utilized a stoichometric amount of aluminium chloride promoter <19920PP463>. Recently, however, A -ethyl phenethylsulfamoyl chloride 214 was shown to undergo Friedel-Crafts cyclization to form sultam 215 with just a catalytic amount of In(OTf)3 (Equation 33) <2002SL1928>. 

Among 138 examples of various sulfamoyl compounds, three isohexide derivatives were mentioned. Their preparation started from corresponding free hydroxyl compounds by reaction with sulfamoyl chloride, which itself had been generated in situ from chlorosulfonyl isocyanate. They were claimed for treatment of chronic arthritis and osteoporosis.221 ... 

N 62.18% colorl solid mp 28—29°. Prepn is by reacting sulfamoyl chloride with Na azide in acetonitrile at RT for 24 hrs. After filtn of the by-product solids, the acetonitrile... 

Contrary to earlier suggestions of an SnI pathway for solvolyses of A,A-dimethyl-sulfamoyl chloride (41), the results of an extended Grunwald-Winstein equation treatment of the specific rates of solvolysis of (41) in 32 solvents pointed to an Sn2 pathway. Results of a similar treatment of its rates of solvolysis in a range of solvents supported an SN2 pathway for 2-propanesulfonyl chloride (42).59... 

Di-0-isopropylidene-p-fructopyranose Sodium hydride Sulfamoyl chloride... 

Some interesting intramolecular variants have been reported. For example, homoallylic alcohols (e.g. 139) can be treated with sulfamoyl chloride to form the corresponding sulfamates (140), which then engage in a direct intramolecular copper-catalyzed aziridination mediated by iodosylbenzene <02OL2481>. A carbamate tether is also effective in delivering the nitrene center to the olefin, as is the case with the cyclohexenyl derivative 142, which spontaneously cyclizes in the presence of iodosylbenzene <02OL2137>. The acetoxy-aminoquinazolinone 144 is converted to the lactone 145 via intramolecular aziridination upon treatment with lead tetraacetate and hexamethyldisilazane (HMDS) <02TL2083>. 

Sulfamates are prepared by reaction between an alkyl sulfamoyl chloride and an OH or ONa group. 

Dimethyl propylamine dimethametryn 3 Dimethyl propylamine propamocarb Dimethyl sulfamoyl chloride bupirimate... 

Inasmuch as phosphorus(V) chloride, phosphorus(V) oxytri-chloride, and (trichlorophosphoranylidene)sulfamoyl chloride are all highly sensitive to moisture, operations that cannot be carried out in closed systems must be done in a gloved dry-box. Caution. Contact between any of these substances and water in a closed system can lead to a dangerous explosion ... 

One hundred twenty-five grams (0.5 mole) of (trichlorophos-phoranylidene)sulfamoyl chloride is placed in a 300-ml., threenecked, round-bottomed flask, to which a gas inlet tube, a thermometer, and a Vigreux condenser are attached. To the top of the Vigreux column, a Liebig condenser is attached. This condenser is, in turn, attached to a receiver which is immersed in a Dry Ice-acetone mixture. The outlet from the... 

The mixture remaining in the three-necked flask is stored overnight at 0°. The solid product is then freed of oily contaminants by spreading on clay plates, which are stored in a desiccator. Finally, the solid is washed with 100 ml. of ice water and then dried in a desiccator over phosphorus(V) oxide. The crude product so obtained is recrystallized twice from 10-15 times its weight of n-heptane which has been previously dried over sodium wire. M.P., 144-145°. Yield, based upon (tri-chlorophosphoranylidene)sulfamoyl chloride, is ca. 12 g. (17%). Anal. Calcd. for N3S3O3CI3 N, 14.36 S, 32.87 Cl, 36.36 mol. wt., 292.57. Found N, 14.51 S, 32.44 Cl, 36.84 mol. wt., 300. 

NlCeHsls, 8 189 N(C6Hu)2S02CI Dicyclohexyl-sulfamoyl chloride, 8 110 NCI3, 1 65 NGa, 7 16 NHBrj, 1 62... 

Preparation. The reagent is prepared in 81 % yield by thereaetion of earboethoxy-.sulfamoyl chloride with 2 eq. of triethylamine in benzene solution at 30°. 

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. ... 

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