Azides cerium ammonium nitrate

Carbyl sulfate , see 2,4-Dithia-l,3-dioxane-2,2,4,4-tetraoxide, 0835 Ceric ammonium nitrate, Ammonium cerium(IV) nitrate, see Ammonium hexanitrocerate, 3958 Cerium azide, 3960 Cerium carbide, 0587 Cerium, 3955 Cerium dihydride, 3956 Cerium(III) tetrahydroaluminate, 0089 Cerium nitride, 3959 Cerium trihydride, 3957 Cerium trisulfide, 3961... 

Using ammonium cerium(IV) nitrate (CAN) as the oxidant for the azide anion, the azido radicals are trapped by alkenes, to form, ultimately, /i-azido nitrates84 cerium azide species may be considered as intermediates. Alkenes conjugated with carbonyl groups are recovered intact. The stereochemistry of the adducts from acenaphthylene and indene was trans, as shown by H-NMR studies (/AX < 2 Hz for the acenaphthylene adduct), but with (-Eyi-phenyl-l-propene both syn and anti additions were formed. 

Excess sodium azide in the filtrate was destroyed by treatment with ammonium cerium(IV) nitrate solution according to the procedure described by Lunn, G. Sansone, E. B., In "Destruction of Hazardous Chemicals In the Laboratory" Wiley New York, 1990 p. 44. 

Sodium Azide/Ammonium Cerium(IV) Nitrate. Silyl enol ethers give a-azido ketones on treament with sodium azide and anhydrous ammonium cerium(IV) nitrate in anhydrous acetonitrile (see Eq. 97).297 325 33i With a glycal, the 2-azido-1-hydroxy nitrate derivative is formed.332 Low yields due to hydrolysis of the silyl enol ether may be improved by use of the triisopropylsilyl (TIPS) derivatives,331 although with a sterically encumbered taxane-derived enol ether the TMS derivative gives higher yields than the TIPS derivative.325 The mechanism is believed to involve addition of an azide radical to the double bond. 

Handling, Storage, and Precautions while relatively insensitive to impact, the solid can decompose explosively above its melting point. It forms highly explosive azides with metals such as Cu, Pb, Hg, Ag, Au, their alloys and compounds, and reacts with acids to form hydrazoic acid (HN3) which is a toxic, spontaneously explosive gas. Explosive gem-diazides can be formed in CH2CI2 or other chlorinated solvents and shock or heat sensitive metal azidothioformates in CS2. All work with NaNs and other azides should be conducted on a very small scale behind a shield, in a fume hood. Excess NaNs on flasks, paper, etc. can be destroyed in a fume hood by soaking with acidifled Sodium Nitrite or by oxidation with Cerium(IV) Ammonium Nitrated... 

Treatment of triisopropylsilyl enol ethers of cyclic ketones with ammonium cerium nitrate (3 equiv) and sodium azide (4.5 equiv) in acetonitrile at — 20 °C gave a-azido ketones in good yields124. By varying the ratio of the reagents the yields were lower or the formation of byproducts, difficult to separate, increased. Mixture of diastereomers (ratio not reported) were generally obtained from substituted substrates, except from the bicyclic ketones 16. 

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