Reaction with sulfamide

Shvets, V. F. Lebedev, N. N. About kinetics and mechanism of ethylene oxide reaction with sulfamides and phenols. Proceedings of MKhTI, 1963,(43), 72-77. 

Reactions of ester derivatives 243 with sulfamidate 244 gave the corresponding pyrazinones 245 in excellent yields (Equation 31) <2006BML1207>. 

The best preparation of 130 involves the reaction of sulfamide with PC15 followed by a [5+1] cyclocondensation reaction between the /)/,v(phosphazo)sulfone Cl3P=N-S02-N=PCl3 and hexamethyldisilazane. The reactions of 129 and 130 with nucleophilic reagents have been studied in considerable detail, with emphasis on the regiochemistry.285... 

Burgess reagent, (methoxycarbonylsulfamoyl)triethylammonium hydroxide, usually used for the dehydration of secondary or tertiary alcohols, was successfully employed in the formation of cyclic sulfamidates from the corresponding epoxides. It was further shown that the same reaction with aromatic epoxides resulted in the formation of seven-membered ring systems, for example, 57 (Figure 23) <2003SL1247>. 

The cyclic sulfamidates of the allosamine derivative 126 (see Scheme 18) are prepared by reaction with 1,1 -sulfuryl diimidazole <1996CC127>, and this method seems to be promising for the synthesis of other sulfamidates. 

Fused and nonfused epoxides can be successfully transferred to corresponding cyclic sulfamidates by the reaction with Burgess reagent <2003SL1247>. 

Single crystals of difluoromethane bis(sulfinic acid) anhydride 17 were isolated, after the cesium salt 119 was stored in the presence of traces of water vapor for several weeks <1998JFC(89)55>. Treatment of difluoromethane-l,l-bis(sulfonyl fluoride) 120 with liquid ammonia led to the formation of the cyclic ammonium imide 121 <1997ZNB359, 1997WO9731909>, while reaction of sulfamide 122 with trifluoroacetaldehyde O-ethyl hemiacetal afforded the cyclic aminal 60 (Scheme 41) < 1999S1731 >. 

The palladium(O) catalysed tandem cyclisation of a bromoallene tethered with a sulfamide group 124 gives bicyclic azepines 125. The analogous reaction with Af-tethered bromoallene sulfamide 126 afforded bicyclic diazepine 127 <07CEJ1692>. Condensation of thiaisatoic anhydride with -amino acids proved to be a straightforward method for the synthesis of thieno[3,2-< ][l,4]diazcpin-2,5-dionc analogues 128 <07JOC2662>. 

CSI (57) (see p. 157) is a useful reagent for the synthesis of sulfamides. CSI (57) by sequential treatment with 2-chloroethanol and a primary or secondary amine affords the corresponding chloroethoxycarbonylsulfamide (144). In the reaction with the amine, the sulfonyl chloride is more reactive than the alkyl chloride and is therefore selectively substituted to yield (144) (Scheme 58). 

Sulfamide (136) may be used in the synthesis of nitriles (148) by a one-pot reaction with acid chlorides involving elimination of sulfamic acid (86) (Scheme 60). The reaction is believed to involve the initial formation of the N-acylsulfamide followed by enolisation and subsequent elimination of sulfamic acid (86) (Scheme 60). 

Several sulfamoylamidine derivatives have shown7 activity as histamine H2 receptor antagonists and are valuable as gastric secretion inhibitors (see Chapter 11, p. 232), e.g. 3-(4-thiazolemethylthio) propionamidines (149), prepared by Lewis acid catalysed reaction of the propionitrile (150) with sulfamide (136) (Scheme 61). 

Thiadiazoline and thiadiazolidine dioxide rings are easily opened by reaction with nucleophiles. Thus, taking advantage of the known aminoexchange reactions of sulfamides first reported by Paquin (48AG316), compound 101a could be opened by treatment with amines yielding the... 

Following a rather similar procedure, the reaction of benzoins with sulfamides afforded the thiadiazoline 1,1-dioxides 103 (64JOC1905). 

We have found in our laboratories that the reaction of cyanogen with sulfamide or N-substituted sulfamides in the presence of hydrogen chloride produces, respectively, 3,4-diamino compound 90a (88LA337) or an imino derivative easily hydrolyzed to 89a (Scheme 45). 

On the other hand, imidothiocarbonates 178 react with sulfamoyl chloride to give the sulfamide 179. Reaction with one equivalent of primary amine provides the isourea 180, which can be readily cyclized by refluxing with trimethyl orthoacetate or trimethyl orthoformate to give 177 (R = Me or H, respectively) (Scheme 65). 

Benzothiadiazepine 3,3-dioxides 234 have been prepared following the same pattern from a,a -diamino-o-xylenes and sulfamides (74M114 76IJC(B)766), or by reaction of a,a -dibromo-o-xylene with sulfamides ([4 + 3]), and a,a -diamino-o-xylenes with sulfuryl chloride ([6-1- 1]) (74M114). 

The chemistry of 1,2,4,6-thiatriazines and related compounds began with the synthesis of l,3,5-tris(4-methoxyphenyl)-124,2,4,6-thiatriazine in 1904.4 The saturated ring system, obtained by ring-closure reaction of sulfamides with formaldehyde, was first described in 1946.5 The first practicable synthesis of l/.4,2,4,6-thiatriazines and their structural elucidation was reported in the early 1950s.6-8 The second period of investigations into the synthesis of l/.4,2,4,6-thiatriazines began when methods for the synthesis of halo-substituted thiatriazines were developed in 1972.9-10... 

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