Sodium, azide

Chlorosulfonic acid reacts with sodium azide (one equivalent) in dichloromethane at 30 C to give the azidosulfonate 4 which precipitates out from solution (Equation 11, see also Chapter 6, ref, 12).  

An analogous reaction between sodium azide and excess chlorosulfonic acid (two equivalents) yielded the very reactive addition compound 5 (Equation 12).  

The adduct 5 may be used for the introduction of nitrogen as N3, NH or NCO groups into organic compounds (Chapter 6, ref. 12). 

LABORATORY CHEMICAL SAFETY SUMMARY SODIUM AZIDE  

Physical Properties Colorless crystalline sobd mp 275 °C (decomposes) Readily soluble in water (41.7 g/100 mL at 17 °C) 

Toxicity Data LD50 oral (rat) 27 mg/kg LD50 skin (rabbit) 20 mg/kg TLV-TWA (ACGIH) 0.29 mg/m (ceiling) 

Major Hazards Highly toxic by inhalation, ingestion, or skin absorption. 

Flammability and Explosibility Flammability hazard is low, but violent decomposition can occur when heated to 275 °C. Decomposition products include oxides of nitrogen and sodium oxide. 

While the trifluoroacetolysis of the epimeric pairs of tosylates 369 and 370, 371 and 372 yields different reaction mixtures, the tosylates 371 and 372 interact quite differently with sodium azide in dimethylsulphoxide (i.e. with a strong nucleophile in a medium perfectly solvating carbocations) in this case only the k process is realized, the skeleton is retained and the configuration is inverted 

In 1975 Cristol, after additional research, admitted his earlier monosta scheme of solvolysis to be incorrect and suggested a two-stage scheme including the an intermediate homobenzylic ion this scheme is quite similar to the one proposed 

These results show the advantages of the benzobicyclo[2,2,2]octadiene and the -octene series in studying solvolysis reactions over the norbomane derivatives. When these models are used the exo and endo isomers yield different reaction mixtures which precludes the intermediate formation of a classical cation with the same skeleton. If this is formed at the stage of reaction proceeding along the k, route it results in products with a skeleton other than that of the compounds formed in the k processes. 

Form Supplied in white solid widely available. 

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 

Introduction. The reaction of NaN3 with I2 (releasing N2) is catalyzed by thiols and thiones and this has been used as a spot test for such compounds. NaN3 has been used to assess the interactions between charged sites in myoglobin. 

Eliminative azidation to form a-azidovinyl ketones occurs 

Nucleophilic azide ion displacements are enhanced by polar, aprotic solvents (e.g. DMSO) with which high yield, aryl halide displacement to form even mononitrophenyl azides can occur. Phase-transfer catalysis (permitting the use of less polar solvents) or ultrasonication (for activated primary halides) has also been used. Under such conditions, 8 2 inversion of configuration occurs and this has been observed also for alcohols under Mit-sunobu conditions (Triphenylphosphine, Diethyl Azodicarboxy-late, HN3). Retention is possible where a neighboring group is present.  

CONTACT WITH ACIDS LIBERATES A TOXIC GAS, EXPLOSIVE 

Crystals decompose on heating, sometimes explosively, especially if heated rapidly.1-3 

Carbon Disulfide. Aqueous solution of NaN3 forms explosive mixture with CS2.5 Chromyl Chloride. Interaction of chromyl chloride and sodium azide to form chromyl azide is explosive in the absence of diluent. 

Heavy Metals. Contact of aqueous solutions with heavy metals (brass, Cu, and Pb) may lead to the formation of explosive heavy metal azides (e.g., in plumbing lines).7 

Hydrochloric Acid. A serious explosion occurred when prednisone was treated with sodium azide and concentrated hydrochloric acid.8 

In pnre form or highly concentrated solntion, hydrazoic acid is a dangerous explosive compound. It is unstable and sensitive to heat and shock. The explosion hazard decreases significantly with more dilute solutions. 

It forms shock-sensitive metal azides when react with metal salts, and fluorine azide with fluorine (Lawless and Smith 1968) and susceptible to form chlorine azide and bromine azide with chlorine gas and bromine vapor. All these products can explode violently on impact. With carbon disulfide it forms a violently explosive salt (Mellor 1946 NFPA 1997). 

EPA Classified Acute Hazardous Waste, RCRA Waste Number PI05 

Sodium azide is used in making other metal azides, therapeutically to control blood pressure, as a propellant for automotive safety bags, as a preservative for laboratory reagents, as an analytical reagent, and in organic synthesis. It is also used as an antifading reagent for immunofluorescence (Boeck et al. 1985). 

Sodium azide is a highly toxic compound the order of toxicity is the same as that of hydrazoic acid. It is converted to hydrazoic acid in water. The aqueous solutions of sodium azide contains hydrazoic acid, which escapes at 37°C (98°F), presenting a danger of inhalation toxicity. 

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M.p. —80°C, b.p. 37°C. Prepared from sodium azide and acid or (N2Hj) plus nitrous acid, HNO2. Heavy-metal salts, azides, are used as detonators, alkali metal salts are stable and azides are used synthetically in organic chemistry. 

The azides are salts which resemble the chlorides in solubility behaviour, for example silver azide, AgNj, is insoluble and sodium azide, NaN3, soluble in water. Sodium azide is prepared by passing dinitrogen oxide over molten sodamide ... 

Dinitroaniline from 3 5-dinItrobenzoic acid. Place a solution of 50 g. of 3 5-dinitrobenzoic acid (Section IV, 168) in 90 ml. of 10 per cent, oleum and 20 ml. of concentrated sulphuric acid in a 1-litre three necked flask equipped with a reflux condenser, mechanical stirrer, adropping funnel, and thermometer (FUME CUPBOARD ). Add 100 ml. of clJoroform and raise the temperature to 45°. Stir rapidly and add 17 -5g. of sodium azide in small portions whilst maintaining the temperature at 35-45°. The reaction is accompanied hy foaming, which usually commences after about 3 g. of sodium azide has been introduced. After all the sodium azide has been added raise the temperature so that the chloroform refluxes vigorously and maintain this temperature for 3 hours. Then cool the reaction mixture, pour it cautiously on to 500 g. of crushed ice, and dilute with 3 litres of water. After 1 hour, separate the yellow solid by filtration at the pump, wash well with water and dry at 100°. The yield of 3 5-dinitroaniline, m.p. 162-163°, is 39 g. The m.p. is unaffected by recrystallisation from dilute alcohol. 

Acetanilide from acetophenone. Dissolve 12 g. of acetophenone in 100 ml. of glacial acetic acid containing 10 g. of concentrated sulphuric acid. To the stirred solution at 60-70°, add 9 8 g. of sodium azide in small portions at such a rate that the temperature does not rise above 70°. Stir the mixture with gentle heating until the evolution of nitrogen subsides (2-3 hours) and then allow to stand overnight at room temperature. Pour the reaction mixture on to 300 g. of crushed ice, filter the solid product, wash it with water and dry at 100°. The yield of crude acetanilide, m.p. 111-112°, is 13 g. Recrystallisation from water raises the m.p. to 114°. 

The best azide to use these days is sodium azide (NaNs). It is inexpensive and unwatched. All azides have the potential to explode upon degradation and are toxic to breathe. The methods... 

Alkvl Azides from Alkyl Bromides and Sodium Azide General procedure for the synthesis of alkyl azides. In a typical experiment, benzyl bromide (360 mg, 2.1 mmol) in petroleum ether (3 mL) and sodium azide (180 mg, 2.76 mmol) in water (3 mL) are admixed in a round-bottomed flask. To this stirred solution, pillared clay (100 mg) is added and the reaction mixture is refluxed with constant stirring at 90-100 C until all the starting material is consumed, as obsen/ed by thin layer chromatographv using pure hexane as solvent. The reaction is quenched with water and the product extracted into ether. The ether extracts are washed with water and the organic layer dried over sodium sulfate. The removal of solvent under reduced pressure affords the pure alkyl azides as confirmed by the spectral analysis. ... 

This following article was sent to Strike by Osmium and Feck (are they the same person ). It involves the direct addition of azide to a terminal alkene (you-know-who) by the in situ production of the reactant mercury (II) azide from mercuric acetate and sodium azide (please don t ask) [80]. 

General Procedure - To a solution of 0.3 moles of sodium azide and 0.1 mole of mercuric acetate in 200mL of 50% aqueous tetra-... 

NOTE In the initial testing of any undesireable interaction between Sodium Azide, Acetic Acid and Sulfuric Acid, I mixed 5mL of each into a small cup underneath my "fume hood". Though I smelled nothing, within seconds my head felt like it was expanding, my heart started racing, and I felt more weak and confused than normal. I just barely escaped and recovered in 15 minutes, but, Needless to say, this procedure is a tad on the dangerous side. You have been warned. ... 

The intermediates in making amines are isocyanates (0==C==N) just like the Hofmann Rearrangement. The isocyanates are decomposed with water, just like the Hofmann. In fact, there is a lot of similarity between the Hofmann and the Schmidt reactions. Before I detail the synthesis steps, I should note that if you wish to generate the Hydrazoic Acid in the flask by adding Sodium Azide, you might need a powder addition funnel. This bit of equipment is quite pricey and it s likely you won t have one, so the first part of the synthesis details how to make the Hydrazoic Acid separately. 

Prepare a paste out of 65g Sodium Azide (lm NaN ) and 65mL of water in a beaker. Add 400mL of either Chloroform or Benzene to this paste (depending on what you have available, but be consistent later on) and stir well. Dump this mixture into a round bottom flask situated in an ice/salt bath, drop in a stirrer magnet, attach a Claisen adapter, addition funnel, and thermometer. Let this mixture cool to OC. 

Regioselective 1,4-azidohydroxylation to give 309 takes place by the reaction of the vinyloxirane 308 with sodium azide[188]. The reaction of the cyclopen-tadiene monoepoxide 310 with sodium azide or purine base offers a good synthetic method for the carbocyclic nucleoside 311(189-191]... 

Not many examples of this class of compounds have been reported. They are prepared by the action of sodium azide on 2-diazonium salts of 2-aminothiazole (590, 597, 598). 

Azide ion ( N=N=N ) Sodium azide IS a reagent used for carbon-nitrogen bond formation The product IS an alkyl azide... 

Acrolein (H2C=CHCH=0) reacts with sodium azide (NaNj) in aqueous acetic acid to form a compound C3H5N3O in 71% yield Propanal (CH3CH2CH=0) when subjected to the same reaction conditions is recovered unchanged Suggest a structure for the product formed from acrolein and offer an explanation for the difference in reactivity between acrolein and propanal... 

Alkyl azides prepared by nucleophilic substitution of alkyl halides by sodium azide as shown m the first entry of Table 22 3 are reduced to alkylammes by a variety of reagents including lithium aluminum hydride... 

Acrolein (H2C=CHCH=0) undergoes conjugate addition with sodium azide in aqueous solution to give N3CH2CH2CH=0 Propanal is not an a 3 unsaturated carbonyl compound and cannot undergo conjugate addition... 

Lead Ammonium nitrate, chlorine trifluoride, hydrogen peroxide, sodium azide and carbide, zirconium, oxidants... 

Tosylates of pentaerythritol and the higher homologues can be converted to their corresponding tetra-, hexa-, or octaazides by direct reaction of sodium azide (36), and azidobenzoates of trimethyl olpropane and dipentaerythritol are prepared by reaction of azidobenzoyl chloride and the alcohols in pyridine medium (37). 

Ma.nufa.cture. Lead azide is typically made from sodium azide [26628-22-8] in small (eg, 5 kg) batches buffered by the reaction solutions of lead nitrate or lead acetate ... 

Automobile safety air bags use sodium azide [26628-22-8] NaN, for gas generation. It can be made from hydrazine by refluxing ethyl or Abutyl nitrite with hydrazine hydrate and sodium hydroxide in alcohol (209,210) ... 

Nitric acid may be precipitated by nitron [2218-94-2] (4,5-dihydro-l,4-diphenyl-3,5-phenylimino-l,2,4-triazole). The yellow precipitate maybe seen at dilutions as low as 1 60,000 at 25°C or 1 80,000 at 0°C. To prevent nitrous acid from interfering with the test results, it may be removed by treating the solution with hydrazine sulfate, sodium azide, or sulfamic acid. 

With sodium azide, salts of secondary nitroparaffins rearrange to N-substituted amides (29). With SO2, primary or secondary nitroparaffins give imidodisulfonic acid salts (30). Potassium nitroform reacts quantitatively with nitryl chloride in ether to form tetranitromethane (31). 

The air bag industry has become one of the principal users of pyrotechnic compositions in the world. Most of the current air bag systems are based on the thermal decomposition of sodium azide, NaN, to rapidly generate a large volume of nitrogen gas, N2. Air bag systems must function immediately (within 50 ms) upon impact, and must quickly deploy a pulse of reasonably cool, nontoxic, unreactive gas to inflate the protective cushion for the driver or passenger. These formulations incorporate an oxidizer such as iron oxide to convert the atomic sodium that initially forms into sodium oxide, Na20. Equation 1 represents the reaction. 

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