Azides, organic

Secondary amines having one oi two chiral groups attached to the nitrogen atom are prepared from boronic esters by their conversion into alkyldichlotobotanes, followed by treatment with organic azides (518). The second chiral group can be derived from an optically active azide. 

Addition on to the exocyclic C—C double bond of an alkylideneaziridine also occurs when this compound is allowed to react with organic azides (75JOC2045). The initially formed spirotriazolines (332) are converted into four-membered ring amidines (334) with extrusion of molecular nitrogen. In the case of phenyl azide, the amidine (334) is obtained alongside the triazoline (333). 

Conversion o( organic azides with phosphines or phosphites to Immophosphoranes (phosphazo compounds) and their hydrolysis to amines. 

Caution/ Although the organic azide intermediates used in this procedure ham not shown any explosive hazard under the experimental conditions. 

Similar differences are found for organic azides (e.g. MeN3). In ionic azides (p. 417) the N3 ion is both linear and symmetrical (both N-N distances being 116 pm) as befits a 16-electron species isoelectronic with CO2 (cf. also the cyanamide ion NCN, the cyanate ion NCO, the fulminate ion CNO and the nitronium ion N02 ). 

Similarly, the regiospecific 1,3-dipolar cycloaddition reaction of 1-methyl-1,2-dihydropyridines 41 with cyanogen azide (50a) and selected organic azides 50c and 50g afforded 2-methyl-2,7-diazabicyclo[4.1.0]hept-4-enes 57, which can be elaborated to 1-methyl-l,2,5,6-tetrahydropyridylidene-2-cyanamide (58) and 1-methyl-2-piperidylidenes 59a-d (85CJC2362). 

Another conceptually unique approach in alkene aziridination has come from Johnston s labs. These workers shrewdly identified organic azides as nitrene equivalents when these compounds are in the amide anion/diazonium resonance form. Thus, when a range of azides were treated with triflic acid and methyl vinyl ketone at 0 °C, the corresponding aziridines were obtained, in synthetically useful yields. In the absence of the Bronsted acid catalyst, cycloaddition is observed, producing triazolines. The method may also be adapted, through the use of unsaturated imi-des as substrates, to give anti-aminooxazolidinones (Scheme 4.25) [32]. 

Kuhn A.C. Duckworth, The Preparation of Some New Polyfunct ional Organic Azides—Part 11 , BRL-MR-2384 (1974) 22) Sax (1975),... 

Refs 1) Beil — DADNBU not found DADNPE not found 2) LP. Kuhn A.C. Duckworth, The Preparation of Some New Polyfunctional Organic Azides , BRL Rept No 1607 (1972) also, the following limited distribution Addnl Ref YP. Carignan, Evaluation of Some New Poly functional Organic Azides for Propellant Applications , PATR 4592(1973)... 

Organic azides and isocyanates as sources of nitrene species in organometallic chemistry. S. Cenini and G. La Monica, Inorg. Chim. Acta, 1976,18,279-293 (86). 

A microwave-assisted three-component reaction has been used to prepare a series of 1,4-disubstituted-1,2,3-triazoles with complete control of regiose-lectivity by click chemistry , a fast and efficient approach to novel functionalized compounds using near perfect reactions [76]. In this user-friendly procedure for the copper(l) catalyzed 1,3-dipolar cycloaddition of azides and alkynes, irradiation of an alkyl halide, sodium azide, an alkyne and the Cu(l) catalyst, produced by the comproportionation of Cu(0) and Cu(ll), at 125 °C for 10-15 min, or at 75 °C for certain substrates, generated the organic azide in situ and gave the 1,4-disubstituted regioisomer 43 in 81-93% yield, with no contamination by the 1,5-regioisomer (Scheme 18). 

Triazoles have been obtained via microwave-assisted [3-i-2] cycloaddition, under solvent-free conditions [54], starting from organic azides and acetylenic amides at 55 °C for 30 min (Scheme 23). The complete conversion of the reagents into AT-substituted-1,2,3-triazoles 69 was achieved without decomposition and side products. A control reaction carried out at the same temperature in an oil bath did not give the cycHc products, not even after 24 h of reaction time. 

Iron pentacarbonyl has been shown to be a catalyst for the reaction of organic azides with isocyanides, giving carbodiimides 127) [Eq. (21)]. 

When an eilkali azide is present, dichloromethane and chloroform form explosive organic azides. 

Finally, in some cases diradical negative ions can even be generated directly npon ionization of appropriate precnrsors. For example, nitrene and carbene anions can be formed by El of organic azides, diazo-compounds, and diazirines, whereas Branman and co-workers have reported the formation of oxyallyl anions by El of flnorinated acetyl componnds (Eq. 5.12). ... 

Petrie, M. A. et al., J. Amer. Chem. Soc., 1997, 119, 8802 All salts of this cation were friction and shock sensitive, too sensitive for actual use as explosives. The most sensitive though, with estimated energy of 5.4 kJ/g, not the most powerful, was the perchlorate. Even though prepared on low milligram scale this invariably detonated spontaneously during work-up or soon after. The more powerful dinitramide (5.8 kJ/g) decomposed non-explosively on standing. See other ORGANIC AZIDES... 

See other cyano compounds, high-nitrogen compounds, organic azides... 

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