Sodium azide preparation

Xanthan Solutions. Specimens of xanthan were obtained from Kelco Co. (Kelzan) and from Dr. P. Sandford, then at U.S.D.A. Northern Regional Laboratory, and were purified by the method described by Holzwarth. ( ) An aqueous stock solution containing V 0.5% xanthan was prepared by addition of distilled deionized water that had previously been filtered through 0.1pm Milllpore filters (to remove bacteria, dust, etc.). This solution was dialyzed for four days against filtered distilled deionized water. Other than for the first solutions used for the thermal studies, sodium azide (0.02%) was added to the stock solutions to retard bacterial growth. Solutions at different concentrations were prepared by dilution with 0.02% aqueous sodium azide. Preparations before and at different intervals after filtration were checked for possible bacterial growth by examination of shadowed specimens in a Jeol lOOB electron microscope. Bacterial cells were not seen in xanthan solutions that had been filtered through 0.22)im Milllpore filters these solutions remained sterile for over a month. 

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 ... 

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. 

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). 

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... 

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). 

Diphenyl phosphorazidate is prepared by the action of sodium azide... 

Putrescine dihydrochloride has been prepared by the Hofmann degradation of adipamide 3.. s by the Curtius degradation of adipyl hydrazide through the urethane by the Curtius degradation of adipyl azide obtained from adipyl chloride and sodium azide by the Schmidt degradation of adipic acid with hydrogen azide by the reduction of succinonitrile, succinaldoxime, or 7-phthalimidobutyronitrile with sodium and from N-ben-zoyl-7-iodobutylamine ... 

A solution of hydrazoic acid (prepared from about 30 g sodium azide) in ca. 200 ml chloroform is prepared in a well-ventilated hood. Cholesterol (15 g) is dissolved in the hydrazoic acid solution and 3.5 ml of triethylamine is added. The reaction mixture is then stirred at room temperature while 7 g of A-chlorosuccinimide is added. The reaction mixture is allowed to stand overnight and then the chloroform solution is washed successively with dilute sodium bisulfite, dilute soldium bicarbonate solutions and finally with water. The chloroform extract is then dried (Na2S04) and the solvent removed in vacuo. The residue is crystallized from ethanol to yield ca. 8.5 g of (101) in colorless needles mp 138-139°. The chloro azide is reduced to the aziridine by lithium aluminum hydride according to the foregoing procedure. 

The Cunius degradation of acyl azides prepared either by treatment of acyl halides with sodium azide or trimethylsilyl azide [47] or by treatment of acyl hydrazides with nitrous acid [f J yields pnmarily alkyl isocyanates, which can be isolated when the reaction is earned out in aptotic solvents If alcohols are used as solvents, urethanes are formed Hydrolysis of the isocyanates and the urethanes yields primary amines. 

Another nittogen-containing inflate derivative, trifluoromethanesuifonyi azide, IS prepared by the reaction of triflic anhydride with aqueous sodium azide [775] and IS used as an efficient reagent for the synthesis of alkylazides from alkylanunes (equation 58)... 

Reactions of ionic or covalent azides with chalcogen halides or, in the case of sulfur, with the elemental chalcogen provide an alternative route to certain chalcogen-nitrogen compounds. Eor example, the reaction of sodium azide with cyclo-Sa in hexamethylphosphoric triamide is a more convenient synthesis of S7NH than the S2CI2 reaction (Section 6.2.1). Moreover, the azide route can be used for the preparation of 50% N-enriched S7NH. 

The use of azide reagents is also important for the synthesis of cyclic sulfur(VI)-nitrogen systems. The reaction of SOCI2 with sodium azide in acetonitrile at -35°C provides a convenient preparation of the trimeric sulfanuric chloride [NS(0)C1]3 (Eq. 2.16). " Thionyl azide, SO(N3)2 is generated by the heterogeneous reaction of thionyl chloride vapour with silver azide (Eq. 2.17). This thermally unstable gas was characterized in situ by photoelectron spectroscopy. The phenyl derivative of the six-membered ring [NS(0)Ph]3 can be prepared from lithium azide and PhS(0)Cl. ... 

Sulfanuric halides contain the characteristic group -N=S(0)X- (X = Cl, F). Unlike the isoelectronic cyclophosphazenes (NPClajx (x = 3-17), " only six-membered rings have been well characterized. The sulfanuric halides are colourless solids (X = Cl) or liquids (X = F), which are stable in dry air. Sulfanuric chloride [NS(0)C1]3 is best prepared by treatment of SOCI2 with sodium azide in acetonitrile at -35°C (Eq. 8.16). It may also be obtained as a mixture of a- and yS-isomers in a two-stage reaction from H2NSO3H and PCls. The fluoride [NS(0)F]3 is formed as a mixture of isomers by the fluorination of [NS(0)C1]3 with Sbp3. ... 

No other compounds which were considered to be thiatriazoles had been prepared at this time. However, one other thoroughly investigated compound, the reaction product of carbon disulfide and sodium azide, which had generally been considered as azidodithiocarbonic acid, was shown by Lieber et al. to be a thiatriazole. 

Sodium azide does not react with carbonyl sulfide to form 5-hydroxy-1,2,3,4-thiatriazole, nor with carboxymethyl xanthates, RO-CS SCH2COOH, to form 5-alkoxy-l,2,3,4-thiatriazoles. The latter, however, could be prepared from xanthogenhydrazides (RO-CS NHNH2) and nitrous acid. They are very unstable and may decompose explosively at room temperature only the ethoxy compound (6) has been examined in detail. This is a solid which decomposes rapidly at room temperature and even at 0°C is transformed after some months into a mixture of sulfur and triethyl isocyanurate. In ethereal solution at 20° C the decomposition takes place according to Eq. (16)... 

The Schmidt reaction of ketones works best with aliphatic and alicyclic ketones alkyl aryl ketones and diaryl ketones are considerably less reactive. The reaction is only seldom applied to aldehydes as starting materials. The hydrazoic acid used as reagent is usually prepared in situ by treatment of sodium azide with sulfuric acid. Hydrazoic acid is highly toxic, and can detonate upon contact with hot laboratory equipment. 

Forster and van Gelderen have prepared a characteristic nitro-derivative of dipentene by treating dipentene nitrosochloride with sodium azide.. The resulting body, C (,H 5(NOH)N3, dipentene nitroso-azide. melts at 72° to 73°. The corresponding active limonene derivatives melt at 52° to 53°. 

In a 1-1. three-nccked, round-bottomed flask equipped with a mechanical stirrer, reflux condenser, and powder funnel are placed 180 ml. of reagent grade chloroform, 16.0 g. (0.16 mole) of cyclobutanecarboxylic acid (Note 1), and 48 ml. of concentrated sulfuric acid. The flask is heated in an oil bath to 45-50°, and 20.0 g. (0.31 mole) of sodium azide (Note 2) is added over a period of 1.5 hours (Note 3). After the addition of sodium azide is complete, the reaction mixture is heated at 50° for 1.5 hours. The flask is cooled in an ice bath, and approximately 200 g. of crushed ice is added slowly. A solution of 100 g. of sodium hydroxide in 200 ml. of water is prepared, cooled to room temperature, and then added slowly to the reaction mixture until the pH of the mixture is approximately 12—13. The mixture is poured into a 2-1. three-necked, round-bottomed flask, the... 

Sodium azide, reaction with l butyl chloroacetate, 46, 47 reaction with diazomum salt from o amino-f> -ni trobiphcny L, 46, 86 Sodium chlorodifluoroacetate, 47, SO reaction with tnphenylphosphme and benzaldehyde, 47, SO Sodium ethoxide, 46, 2S reaction with diethyl succinate, 46,2S Sodium formate as reducing agent in preparation of palladium catalyst, 46, 90... 

Prepared from 40 g of sodium hydroxide, 20 g of potassium iodide and 0.5 g of sodium azide made up to 100 mL with water. 

CAUTION All azides, particularly low molecular weight acyl and alkyl azides, are explosive, and great care should be taken while preparing and handling these materials. In addition, hydrazoic acid, which is liberated from unbuffered aqueous solutions of sodium azide, is highly toxic and all operations involving its use should be carried out in an efficient fume hood. 

Several 5,6-disubstituted-3-azido[l,2,4]triazine-l-oxides 1021 were prepared (77JHC1221) by treatment of 1020 with nitrous acid. 3-Azido[l, 2,4]-triazine-2-oxide 1023 was prepared by reacting the corresponding 3-bromo derivative 1022 with either tetramethylguanidinium azide in chloroform or sodium azide in aqueous acetone. These azido derivatives were proven to exist in the open-chain form by H- and l3C-NMR and 1R spectra (77JHC1221) (Scheme 191). 

Watt and coworkers139 prepared the a-azidoaldehydes (242) by nucleophilic ring opening with sulfinate ion expulsion of a, /(-epoxy sulfones 241 with sodium azide in DMF... 

The azide ion is a highly reactive polyatomic anion of nitrogen, N3 . Its most common salt, sodium azide, NaN3, is prepared from dinitrogen oxide and molten sodium amide ... 

A microwave-assisted three-component reaction has been used to prepare a series of 1,4-disubstituted-1,2,3-triazoles with complete control of regiose-lectivity by click chemistry , a fast and efficient approach to novel functionalized compounds using near perfect reactions [76]. In this user-friendly procedure for the copper(l) catalyzed 1,3-dipolar cycloaddition of azides and alkynes, irradiation of an alkyl halide, sodium azide, an alkyne and the Cu(l) catalyst, produced by the comproportionation of Cu(0) and Cu(ll), at 125 °C for 10-15 min, or at 75 °C for certain substrates, generated the organic azide in situ and gave the 1,4-disubstituted regioisomer 43 in 81-93% yield, with no contamination by the 1,5-regioisomer (Scheme 18). 

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