Nitroalkanes azides

In general, C-nitro compounds are more stable than /V-nitro compounds because of the higher bonding energies in the former type. Evidence is offered [1] that decomposition and explosion of many nitro-derivatives proceeds through the aci-form, and that sensitivity corresponds to the proportion of that present. In terms of this work, sensitisation by very small proportions of soluble organic bases is most important this is not limited to nitroalkanes. TNT can apparently be brought to the sensitivity of lead azide by this means. For a physicist s view of this sensitisation,... 

Bowman and co-workers synthesized 2-azido-2-nitropropane by treating the sodium salt of 2-nitropropane with a mixture of sodium azide and potassium ferricyanide. Olah and co-workers used the same methodology for the synthesis of alicyclic gem-azidonitroalkanes from secondary nitroalkanes. Isomeric azidonitronorbornanes (38) and (39) were synthesized from 2,5-dinitronorbornane (37). Some of the gem-azidonitroalkanes synthesized during this work have poor chemical and thermal stability. 

Alan H. Haines, Methods for the Oxidation of Organic Compounds, Alcohols, Alcohol Derivatives. Alkyl Halides, Nitroalkanes, Alkyl Azides, Carbonyl Compounds, Hydroxyarenes and Amino-arene s, 1988... 

Thiophosphite ion, even upon irradiation, only attacks the halogen atom of Me2C(Cl)N02 in an S 2 attack on the halogen188. With azide anion as nucleophile, only low yields of substitution products have been obtained287,288. Much more effective nitrogen--centred nucleophiles in photostimulated reactions with a-halo nitroalkanes are the anions of nitroimidazoles186 and imidazoles187. With the ambident 4(5)-nitroimidazole anion, the 4-isomer is exclusively formed, with no indication of the 5-isomer (equation 72). 

The reaction of nitroalkanes and dinitroalkanes with sodium hydrogen telluride gives nitrosoalkane dimers and olefins, respectively.96 The reduction of other nitrogenated species such as hydroxylamines, azides, nitroso, azo, and azoxy compounds can also be performed by using tellurium reagents.6,11,12... 

Primary and secoiidary nitroalkanes. A new route to nitro compounds involves conversion of azides to phosphine imines by reaction with triphenyl- or tri-n-butylphos-phine at 25—35° followdd by ozonolysis in CHiCE at — 78°. Presumably the initial ozonidc is converted into a nitfoso compound, which is then oxidized to the nitro compound... 

An electro-oxidation procedure developed by Wright for the synthesis of azides from salts of carboxylic acids or nitroalkanes (equations 147, 148) has been briefly referred to by Smith in a recent review . ... 

Cleavage of C-N bonds has been described elsewhere, for example, the reduction of g wj-dinitroalkanes to nitrite ion and nitroalkane anion [181,182] and f-nitroalkanes to nitrite and alkyl radical (Chapter 9) and the reduction of pyridylamines to picoline and ammonia (Chapter 18) [13,14] a rare case of a reductive loss of a nitro group from a benzene ring in l,2,4,5-tetrafluoro-3,6-dinitrobenzene has been reported [183]. Reduction of activated azides yields azide ion phenacyl azide is thus reduced to acetophenone and azide [236]. 

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