Azide, Benzenesulfonyl

Di-(ert-butyl malonate Malonic acid, di-terf-butyl ester (8) Pro-panedioic acid, bis(l,l-dimethylethyl)ester (9) (541-16-2) p-ToIuenesulfonyl azide (8) Benzenesulfonyl azide, 4-methyl- (9) (941-55-9)... 

Electrophilic addition to spiro phosphenium cations 258 provides a route to spirophosphoranes. However, only very active electrophiles are suitable, for example, benzenesulfonyl azide which on reflux in acetonitrile with 258 yields 259 (Equation 70) <1998RJC530>. 

The first metal-catalyzed nitrogen atom-transfer process was reported by Kwart and Khan, who demonstrated that copper powder promoted the decomposition of benzenesulfonyl azide when heated in cyclohexene.280 Evans has demonstrated that Cu(i) and Cu(n) triflate and perchlorate salts are efficient catalysts for the aziridination of olefins employing TsN=IPh as the nitrene precursor.281 Subsequent to this finding, intensive effort has focused on the identification of... 

Acetyl azide, 0771 A-Azidocarbonylazepinc, 2728 Azidocarbonyl fluoride, 0339 Azidocarbonylguanidine, 0820 4-Azidocarbonyl-1,2,3-thiadiazole, 1069 Azidodithioformic acid, 0386 Benzene-l,3-bis(sulfonyl azide), 2210 Benzenesulfinyl azide, 2273 Benzenesulfonyl azide, 2274 Benzoyl azide, 2698... 

Work originally described by Kwart and Khan is often cited as the first example of a nitrene reaction performed under the influence of a transition metal ion [13, 14]. In these experiments, benzenesulfonyl azides were heated in the presence of copper pow-... 

If metal carbene chemistry can be said to be mature, metal nitrene chemistry is in its infancy. Although the first report of a catalytic process used benzenesulfonyl azide,high temperatures were required, and no one has yet provided a synthetically viable method to use azides as sources of nitrenes. Instead, iminophenyliod-inanes (44), formed from the corresponding sulfonamide by oxidation with... 

Benzenesulfonyl azide has been reported [20] to decompose violently on heating, especially if it is in the dry solid state. 

Kwart and Kahn have found that benzenesulfonyl azide forms a complex with freshly reduced copper powder.189 190 This copper azide complex decomposes at a lower temperature than the pure sulfonyl azide. In refluxing methanol, benzene-sulfonamide (27) is isolated as the major product. In the presence of dimethyl sulfoxide, N-benzenesulfonyldimethyl-sulfoximine (28) is obtained in almost quantitative yield. In cyclohexene solution benzenesulfonamide (29), N-benzenesul-fonyl-7-azabicyclo[4.1.0]heptane (30), and 1-cyclohexenylben-zenesulfonamide (31) are isolated as the main reaction products. According to the authors, Schemes VII and VIII represent an acceptable interpretation of the experimental data.189 190 In pure alcohol, the decomposition should occur by two competitive reactions (Scheme VII) producing benzenesulfonamide together with a ketone and oxidized copper. These last two products have indeed been observed in the reaction mixture. In the presence of DMSO, it seems that a copper-nitrene intermediate is formed which is trapped by DMSO. In cyclohexene solution, the authors have observed that the aziridine (30) disappears from the product composition when DMSO is added. The yield of enamine 31, however, is... 

By treating norbornene with benzenesulfonyl azide in benzene at room temperature, a crystalline product is obtained in quantitative yield.264-265 On the basis of chemical and nmr evidence, an aziridine structure (85) similar to exo-2,3-epoxy-norbornene (86) is attributed to the adduct. The addition thus occurs at the least hindered exo side of the bicyclic nucleus. 

Benzenesulfinyl azide, 2266 Benzenesulfinyl chloride, 2227 Benzenesulfonic anhydride, 3492 Benzenesulfonyl azide, 2267 Benzenesulfonyl chloride, 2228... 

Azidocarbonylguanidine, 0816 Azidodithioformic acid, 0385 Benzene-1,3-bis(sulfonyl azide), 2203 Benzenesulfinyl azide, 2266 Benzenesulfonyl azide, 2267 Benzoyl azide, 2694... 

The mixture 258 was converted to the unstable benzenesulfonyl aziridine 259 by treatment with an excess of benzenesulfonyl azide in benzene. Ace-tolysis of 259 with acetic acid and sodium acetate at room temperature for several days afforded the crystalline mixture of diastereoisomers represented by the formula 260. The aziridine rearrangement was regiospecific and 260 was the only product detected during this rearrangement. Lithium aluminium hydride reduction of 260 followed by acetylation yielded the mixture 261 in 85% yield. Selective hydrolysis of 261 afforded 262 in quantitative yield. The diastereoisomeric mixture 262 was converted into the diols 263 by hydrogenolysis. The diol mixture was oxidized with chromium trioxide... 

The reaction of cyclic 1,1-enediamines 7 and 8 with azides appears interesting. Nitro-substituted 1,1-enediamines 7 reacted with benzenesulfonyl azide to give triazoles 225 in moderate yields. Other secondary 1,1-enediamines analogues gave similar products in comparable yields. The reaction has been postulated to proceed by a sequence of 1,3-cycloaddition to 223, a Dimroth rearrangement to 224 and deamination to 225 (Scheme 12)174. Junjappa and coworkers175 have reported that 1,1-enediamines... 

In contrast to benzenesulfonyl azide, the reaction between 8 and aryl azides gives only a small amount of 226. Instead, highly substituted triazoles 228 are formed as the major products176,177. When 4-nitrophenyl azide is used, the reaction furnishes 228 exclusively. It has been believed that the reaction involves two competitive pathways and benzoyl-substituted 1,1-enediamines 8 act mainly as nucleophiles rather than as 1,3-dipolarophiles toward aryl azides. Consequently, they add to the azide group and, following intramolecular cyclocondensation, give products 228. Only in the case of unfavorable electronic factors does 1,3-cycloaddition reaction to give 226 take place (Scheme 13)177. 

Acetamidobenzenesulfonyl azide is obtained from Aldrich Chemical Company, Inc., and used without further purification. In addition, 4-acetamido-benzenesulfonyl azide can be synthesized from the precursor, 4-acetamidobenzene-sulfonyl chloride.2... 

Ollivier and Renaud built on his new ditin-mediated radical azidation with benzenesulfonyl azide [125] to introduce tandem intramolecular cyclization-azidation processes [126]. For example, iodoacetal 131 provides the corresponding tertiary azide 132 in high yield as a 3 2 mixture of endolexo diastereoisomers (Scheme 41). The necessify of using ditin reagents still constitutes a drawback in this method, as DLP-mediated tin-free reaction conditions failed due to an inefficient chain process. 

Similarly, 1,3 -dipolar cycloadditions of benzenesulfonyl azides to N,N- diethylaminoprop-1-yne led to 1,2,3-triazoles (72a) and a-diazoamidines (72b). With the aid of IR and H NMR data these were shown to exist in a tautomeric equilibrium (70JOC3444). With IR and H NMR data a 5-aminotriazole-diazoamidine equilibrium (73a) s (73b) was established (70TL2823, 72CB2963, 72CB2975). However, 4-amino-l,2,3-triazole (74a) proved to be stable and no ring-chain tautomerism could be identified (73TL1137). 

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