Carbonyl azides

Tests conducted by the Eastman Kodak Company have shown that tert-butyl azidoformate [Formic acid, azido, -butyl ester], also known as iert-butoxy carbonyl azide and 1-BOC azide, is a thermally unstable, shock-sensitive compound (TNT equivalence 45%). 

Dunethoxy-4-methyl-3-oxo-3,4-dihydro-2-quinoxalmecarbonyl chloride (92, R = Cl) gave the corresponding carbonyl azide (92, R = N3) (NaN3, AcMe,... 

N-benzylaniline with phosgene, and then with sodium azide to produce carbonyl azide 52. On heating, nitrogen is evolved and a separable mixture of nitrene insertion product 53 and the desired ketoindazole 54 results. The latter reaction appears to be a Curtius-type rearrangement to produce an N-isocyanate (54a), which then cyclizes. Alkylation of the enol of 54... 

Rearrangement reactions have provided access to some interesting azepinone or azepine dione systems. Curtius rearrangement followed by a [3,3] sigmatropic reaction on intermediate carbonyl azides gave azepin-2-one derivatives, for example 2, in fair to moderate yield. The precursor intermediates for this sequence were made, in turn, by treatment of 2-siloxysubstituted 2-alkenylcyclopropanecarboxylic acids (for example, 1) (Scheme 1) with diphenylphosphorazidate and triethylamine <00SL725>. 

Kumar and Ramakrishnan synthesized hyperbranched polyurethanes via the in-situ generation of 3,5-dihydroxyphenyl isocyanate from the corresponding carbonyl azide [98]. The degree of branching was determined as being close to 0.6 using NMR spectroscopy. The hyperbranched polyurethane was completely soluble in common organic solvents while the linear counterpart was completely insoluble. 

The pyrrole derivative of carbonyl azide 206 undergoes thermal Curtius rearrangement into isocyanate, which spontaneously cyclizes into pyrrolo-diazepinone 207 (Equation (27) (1991JHC1911)). 

Dioxo-l,2,3,4-tetrahydrophtho I azin- 5-carbonyl Azide [called 1.4-Dioxo-1.2.3.4-... 

Dioxo-l, 2, 3,4-tetrahy drophthalazin-5 -carbonyl azide 5 D1406... 

Routes to AH-1,3-oxazines and -thiazines involve the cyclization of amides or thioamides with acidic reagents (Scheme 35) (78AHC(23)l). l,3-Oxazin-2-ones can be made by the thermolysis of carbonyl azides (262 Scheme 36) (79CC719). 

Butyrolactone - a carbonyl Azide(called Butyrolacton-a-carbonsaure-azid in Ger), CH2.CH2.CH.CON3 mw 155.11, N 27.09% yel... 

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

Carbohydrazide is not an expl, but in the presence of nitrous acid is converted into the highly expl Carbonyl Azide, C0(N3)2(See Vol 1, p A528- L)... 

McKeone et al. proposed to use 7-methoxy coumarin-3-carbonyl azide (7-MCCA) to prepare fluorescent derivatives to be detected with absorption at 340 nm and emission at 370 nm (91). Reversed-phase HPLC was carried out with A/2-P/W (64/25/11) some typical chromatograms are shown in Fig. 8. 

The preliminary enzymatic hydrolysis step can be omitted in the case of lysoPL. The latter may be derivatized at the sn-2 position of the glycerol group by 7-diethylaminocoumarin-3-carbonylazide (94). According to McKeone et al., however, 7-MCCA proved to be better suited than 7-diethylaminocoumarin-3-carbonyl azide, even though the latter had a higher molar extinction coefficient (91). 

Fig. 8 Serum PC molecular species distribution after 6 weeks of treatment for both the placebo control group (A) and the drug-treated group (B). The molecular species were derivatized with 7-methoxycoumarin-3-carbonyl azide prior to analysis and detected by fluorescence with excitation at 340 nm and emission at 370 nm. (Reprinted from Ref. 91 with the permission of the Journal of Lipid Research.)...

Savb et al. (2006) report a method to evaluate micelle integrity irottitro andin vivo. PEO-b-PCL micelles were synthesized with a Luorogenic dye, Luorescein-5-carbonyl azide diacetate, covalently attached to the PCL block. In the hydrophobic core of intact micelles, the dye remained... 

Reduction of multiple bonds with samarium diiodide has been reviewed. Chemo-and stereo-selective reduction of various compounds such as conjugated alkenes, c/,/3-unsaturated carboxylic acids, activated alkynes, carbonyl, azides, nitriles, and nitro compounds, under mild conditions, has been discussed. Recent developments in the use of samarium metal in this field have also been discussed.381... 

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],... 

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