Copper azide, decomposition

Kwart and Khan investigated the copper-catalyzed decomposition of benzenesulphonyl azide both in methanol 33) and in cyclohexene 34>. No reaction occurs between benzenesulphonyl azide and cyclohexene at 100 °C but the addition of copper powder causes a smooth decomposition to take place yielding an impressive array of products 34>. The major ones are benzenesulphonamide 18 (37%), the aziridine 19 (15%) and the lV-(l-cyclohexenyl)benzenesulphonamide 20 (17%) (Scheme 2). Some traces of cyclohexyl azide were also found but the addition of hydro-quinone eliminated its formation. 

Dimethyl sulphoxide (amounting to slightly more than equimolar with azide and less than 1% overall concentration in solution in methanol) accelerates the copper-catalyzed decomposition and the only product formed (97%) is the sulphoximine (21). Even in the absence of copper, DMSO and benzenesulphonyl azide were found to undergo a slow reaction in boiling methanol to give 21 (< 40%). It was suggested33) that the sulphonyl azide itself (slow) or the copper complex 24 (fast)... 

On the other hand, thermolysis of ferrocenylsulpkonyl azide (14) in aliphatic solvents may lead to the predominant formation of the amide (16) 17>. A 48.4% yield of (16) was obtained from the thermolysis in cyclohexane while an 85.45% yield of 16 was formed in cyclohexene. Photolysis of 14 in these solvents led to lower yields of sulphonamide 32.2% in cyclohexane, 28.2% in cyclohexene. This suggests again that a metal-nitrene complex is an intermediate in the thermolysis of 14 since hydrogen-abstraction appears to be an important made of reaction for such sulphonyl nitrene-metal complexes. Thus, benzenesulphonamide was the main product (37%) in the copper-catalyzed decomposition of the azide in cyclohexane, and the yield was not decreased (in fact, it increased to 49%) in the presence of hydroquinone 34>. On the other hand, no toluene-sulphonamide was reported from the reaction of dichloramine-T and zinc in cyclohexane. 

Addition of carbethoxynitrenes to olefinic double bonds occurs readily. Addition of both the singlet and the triplet species can take place, the former stereospecifically, the latter not 49>. Additions of sulphonyl nitrenes to double bonds have not been demonstrated except in two instances in which metals were present. The reason is that either addition of the starting sulphonyl azide to the double bond occurs to give a triazoline that loses nitrogen and yields the same aziridine as would have been obtained by the direct addition of the nitrene to the olefin, or the double bond participates in the nitrogen elimination and a free nitrene is never involved 68>. The copper-catalyzed decomposition of benzenesulphonyl azide in cyclohexene did give the aziridine 56 (15%), which was formulated as an attack by the sulphonyl nitrene-copper complex on the double bond 24>. 

Scheme 17.1 Copper-catalyzed decomposition of arylsulfonyl azides.

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... 

CuN3 (c). Wohler and Martin1 measured the heat of decomposition of copper azide to be 56.8. 

The copper-catalysed decomposition of benzenesulphonyl azide in cyclohexene gave a variety of products (equation 182) . In the presence of hydroquinone, cyclohexyl azide was not observed. It was assumed that cyclohexanone came from the hydrolysis of the imine (405). The copper-catalysed decomposition of 2-biphenylylsulphonyl... 

Scheme 12.2 Copper catalyzed decomposition of benzenesulfonyl azide leads to a mixture of C H amination and aziridination products.

Copper-catalyzed decomposition of tosyl azide or chloramine T in the presence of DMSO leads to A -tosylsulfoximines (149-151). The configuration of sulfur is retained (150). Thus, the nitrenoid intermediates are trapped by the... 

Copper-catalyzed decomposition of benzenesulfonyl azide in the presence of cyclohexene was the first reported evidence of a metal-catalyzed nitrene insertion reaction [25]. This seminal discovery was then followed by the pioneering work of Breslow and Gellman who introduced the use of iminoiodinanes as metal nitrene precursors as well as rhodium dimer complexes as catalysts [26,27]. They showed the formation of the corresponding benzosultam in 86% yield in the presence of rhodium (II) acetate dimer (Rh2(OAc)4) via an intramolecular metal nitrene C—H bond insertion reaction (Eq. (5.1)). 

Silver azide is often reported as being compatible with most usual metals, even though it reacts with the two most common ones—copper and aluminum. Taylor does not mention aluminum and reports that among common metals only copper reacts under moist conditions [71], Blay and Rapley reported that copper azides form when SA comes into contact with copper in moist conditions [36]. They further reported that SA reacts with aluminum as well. The corrosion of aluminum is quite fast but requires water in liquid phase in direct cmitact with both SA and aluminum. This is not the situation that would normally be found inside a detonator and, if it were the case, then the presence of liquid water would cause the detonator to fail for other reasons than corrosion. A humid environment itself is not sufficient to cause any significant degree of reaction and the use of SA in aluminum detonators has not presented a problem [36]. The decomposition products of SA are not hazardous substances and mainly cmitain metallic silver [36]. 

Todd, G., Father, R., Heron, T. The decomposition of lead azide under storage conditimis. In Proceedings of Symposium on Lead and Copper Azide, pp. B-2, 34-44, Waltham Abbey, 1966... 

Kwart H, Khan AA. Copper-catalyzed decomposition of benzenesulfonyl azide in cyclohexene solution. J/lm Chem Soc. 1967 89 1951-1953. 

Copper catalyzes the decomposition of sulphonyl azides in benzene very slowly. When methanesulphonyl azide was boiled under reflux in benzene solution in the presence of an excess of freshly reduced copper powder, some decomposition occurred to give methanesulphonamide and azide was recovered 78>. Transition metal complexes have been found to exert a marked effect upon the yields of products and isomer ratios formed in the thermal decomposition of methanesulphonyl azide in methyl benzoate and in benzotrifluoride 36>. These results will be discussed in detail in the section on the properties of sulphonyl nitrenes and singlet and triplet behaviour. A sulphonyl nitrene-iron complex has recently been isolated 37> and more on this species will be reported soon. 

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... 

Decomposition of sulfonyl azides was shown to be catalyzed by copper in 1967 (72, 73). In the presence of alkenes, the reaction provides both aziridines and the C-H insertion products, albeit in low yields (73). In 1991, Evans et al. (74, 75) illustrated that both Cu(I) and Cu(II) salts were effective catalysts for nitrenoid transfer from [A-(/Moluenesulfonyl)imino]phenyliodinane (PhI=NTs) to a variety of acceptor alkenes. In the absence of ancillary ligands, reactions proceed best in polar aprotic solvents such as acetonitrile. Similar results are observed using both Cu(MeCN)4C104 and Cu(acac)2 as precatalysts, Eq. 53. 

Kabanov, A. A. etal., Russ. Chem. Rev., 1975, 44, 538-551 Application of electric fields to various explosive heavy metal derivatives (silver oxalate, barium, copper, lead, silver or thallium azides, or silver acetylide) accelerates the rate of thermal decomposition. Possible mechanisms are discussed. 

OpticaUy active iV-tosylsulfoximides produced in the copper-catalyzed reaction of chiral sulfoxides with tosyl azide may be hydrolyzed with strong acid (H2SO4) to optically active free sulfoximides. However, this procedure often fails and/or results in decomposition. It is interesting to note in this connection that a simple one-step method for the preparation of optically active unsubstituted sulfoximides has been reported recently by Johnson and co-workers (180). It involves the reaction between optically active sulfoxides and 0-mesi-tylsulfonylhydroxylamine and results in sulfoximides 60 of high optical purity. As expected, this imidation process occurs with retention of configuration at sulfur. 

Sodium azide is a toxic as well as an explosive substance (Patnaik, P. 1999. A Comprehensive Guide to the Hazardous Properties of Chemical Substances, 2nd e(j New York John Wdey Sons). Although inert to shock, violent decomposition can occur when heated at 275°C. Contact of solid or solution with lead and copper must be avoided. Reactions with halogens, carbon disulfide, or chromyl chloride can be explosive. Dissolution in water produces toxic vapors of hydrazoic acid. The salt is an acute poison causing headache, hypotension, hypothermia, and convulsion. 

Violent reaction with benzoyl chloride combined with KOH, Bt2, barium carbonate, CS2, Cr(OCl)2, Cu, Pb, HNO3, BaCOs, H2SO4, hot water, (CH3)2S04, dibromomalononitrile, sulfuric acid. Incompatible with acids, ammonium chloride + trichloroacetonitrile, phosgene, cyanuric chloride, 2,5-dinitro-3-methylbenzoic acid + oleum, trifiuroroacryloyl chloride. Reacts with heavy metals (e.g., brass, copper, lead) to form dangerously explosive heavy metal azides, a particular problem in laboratory equipment and drain traps. When heated to decomposition it emits very toxic fumes of NOx and Na20. See also AZIDES. 

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