Carbonyl Diazide

A very reactive nitrogen atom is required to convert benzenes or naphthalenes into pyridines, and there are a number of such reactions which involve nitrenes or nitrenoid species. A number of substituted benzenes have been treated with sulfonyl diazide or carbonyl diazide and moderate yields of pyridines recorded (27CB1717). Thus p-xylene gives 2,5-dimethylpyridine there is no indication of the fate of the carbon atom which is lost. More controlled reaction is possible in intramolecular insertions. The examples in which o-nitrotoluene is converted into a derivative (759) of 2-acetylpyridine, and where 2,3-diazidonaphthalenes give 3-cyanoisoquinolines (760) are quoted in a review (81 AHC(28)231>. 

Carbonyl Diazide (formerly called Carbonyl Nitride Carbazoimide) (Called Rohlensaure diazid, Carbazid or Sticks to ffkohlenoxyd in Ger), C0(Ns)jr mw 112.06, N 75.00% extremely volat, long ndls very sol in w, ale and eth but insol in petr eth undergoes hydrolysis to yield C03 and HN3 it has a penetraring odor and like other carbonyl compds is highly toxic and dangerous (Ref 7)... 

Carbonyl diazide is an extremely dangerous expl as it may explode violently, even under H O, on si friction or when exposed to light... 

Carbazido One of the Ger names for Carbonyl Azide or Carbonyl Diazide described in Vol I,p A528-L... 

Carbonyl Diazide A528 L Cellulose Triacetate. See under Acetyl Celluloses A55-R Cerium Azide A528-R Cerium Hydroxydiazide A528-R Cerium Triazide A528-R Cesium Azide A528-R Cesium Carbide A72 L Chain Reaction. See under Atomic Energy A501-L... 

Most organic azides do not possess the properties required for primary explosives and generally can be characterized by low physical and chemical stability (lower alkyl azides, sulfuryl azide explode even spontaneously [8, 11]), high sensitivity to mechanical stimuli (lower aUcyl azides, acyl azides e.g., carbonyl diazide explode on contact with a glass rod [30]), low thermal stability (e.g., cyanogen azide, l,3,5-triazido-2,4,6-trinitrobenzene, dicyanamid azide, esters of azidoacetic acid [8]), or sensitivity to light [127]. 

The carboxylic acid derivatives li-lm can only be matrix-isolated if the corresponding quinone diazides 2i-2m are irradiated with monochromatic blue light (k = 436 nm).81 91 92 UV or broad-band visible irradiation rapidly results in the decarboxylation of the carbenes. As expected, the IR and UV/vis spectra of the carbenes are very similar to that of la. Oxygen trapping results in the formation of the photolabile carbonyl oxides 7. Thus, the carbenes li-lm were identified both spectroscopically and by their characteristic reaction with molecular oxygen. 

The Wolff rearrangement is well known as a reaction of diazo ketones, i.e. of diazoalkanes with a carbonyl group in a-position. Reaction 34 demonstrates that diazotized aminonaphthols are mesomeric with naphthoquinone diazides (48b) and that they have therefore also the character of quinonoid diazo ketones (see also Section II.C of this chapter). Wolff rearrangements take place also thermally and catalyzed by silver ions. 

Trituration of the crude cw-azide with hexane at ambient temperature caused detonation to occur. Isolation of low molecular weight carbonyl azides should be avoided, or extreme precautions taken. A similar incident with the analogous cyclobutane diazide was reported [1], During use as an intermediate in preparation of the 1,2-diamine, the explosive diazide was never isolated or handled free of solvent [2]. The trans isomer (0.25 mole) was prepared by the latter technique, but as a 45 w/v% solution in toluene, rather than as the recommended 10% solution. When a magnetic spin-bar was introduced, the solution detonated. Initiation may have involved friction from adventitious presence of iron filings adhering to the magnetic bar [3],... 

Phenylthallium diazide, 2279 Phenylthiophosphonic diazide, 2278 Phenylvanadium(V) dichloride oxide, 2239 Phosgene, see Carbonyl dichloride, 0328 Phospham, 4434 f Phosphine, 4503... 

The difference is interestingly exemplified in the differing modes of reaction of hydrazoic acid with some alkylidene (and arylidene) oxazolone derivativesThe alkylidene compound 174 behaves as an a, -unsaturated carbonyl compound with the hydrazoic acid adding to the exocyclic double bond. A subsequent ring opening with further addition leads to the formation of the diazide 175 (equation 75). In contrast the exocyclic double bond of the arylidene compound 176 is unreactive, and nucleophilic attack occurs at the... 

Acetyl azide has been prepared only in solution ". Propionyl azide is a colourless liquid of pungent odour, the inhalation of which causes severe headaches. Higher fatty acid azides have been obtained by distillation at 0° and 0-5 mm Hg and their infrared spectra measured neat (Table 1). rv-Hexanoyl azxde shows i.r. bands at 2130 and 1720 cm in cyclohexane solution. A number of more complex alkanoyl azides have also been prepared in solution while the azide of tetra-acetyl-D-arabonic acid was isolated crystalline (m.p. 105-6° dec.) ". An example of a more exotic acyl azide is 2,3-diphenyl-cycloprop-2-ene-1-carbonyl azide . The diazide of oxalic acid was isolated crystalline (from CCI4) but exploded when touched with a spatula . Succinamoyl azidea crystalline substance with a decomposition point of 70-80°, undergoes slow Curtius rearrangement already at room temperature, just as the azides of monocarboxylic acids do. 

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