Azides, sodium with

Reaction at position 4 of perfluotopyndme thus occurs readily with nitrogen nucleophiles, as exemplified by its reactions with sodium azide and with hydroxyl-amme [75, 76] (equation 39)... 

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... 

Various nucleophiles undergo addition to oxepins to give functionalized cyclohexadienols. Thus, terf-butyl oxepin-4-carboxylate when treated with a methanolic solution of lithium hydroxide gives /ert-butyl ow .v-5-hydroxy-6-methoxycyclohexa-l,3-diene-1-carboxylate (3a) in 56% yield.156 When dioxane is used as solvent, the respective dihydroxy derivative 3b is obtained in 30 % yield. Sodium azide reacts with oxepin to give mws-6-azidocyclohexa-2,4-dien-l-ol (3c) in 55% yield.212... 

The detection depends on the iodine azide reaction that normally takes place very slowly and during the course of which sodium azide reacts with iodine to form sodium iodide with the production of nitrogen ... 

Sodium azide, reaction with 1-butyl chloroacetate, 46, 47 reaction with diazonium salt from -ammo-/> -nitrobiphcnyl, 46,... 

Sodium, with l-bromo-3-chloro-cyclobutane to give bicyclo [l.l.O]butane, 51, 55 Sodium amalgam, 50, 50, 51 Sodium amide, with 2,4-pentane-dione and diphenyliodonium chloride to give l-phenyl-2, 4-pentanedione, 51, 128 Sodium azide, 50, 107 with mixed carboxylic-carbonic anhydrides, 51, 49 Sodium borohydride, reduction of erythro-3-methanesulfony-loxy-2-butyl cyclobutanecar-boxylate, 51, 12 reduction of 2-(1-phenylcyclo-pentyl)-4,4,6-trimethyl-5,6-dihydro-1,3(4H)-oxazine to 2-(1-phenylcyclopentyl)-4,4, 6-trimethyltetrahydro-l,3-oxazine, 51, 25 Sodium cyanoborohydride, used... 

An excess of sodium azide reacts with 2,3-allenoates to give ,/)-unsaturatcd eno-ates 499. No reaction was observed with 4,4-disubstituted 2,3-allenoates [225]. 

Although aliphatic azides can be prepared under liquidrliquid phase-transfer catalytic conditions [3-5], they are best obtained directly by the reaction of a haloalkane with sodium azide in the absence of a solvent [e.g. 6, 7]. Iodides and bromides react more readily than chlorides cyclohexyl halides tend to produce cyclohexene as a by-product. Acetonitrile and dichloromethane are the most frequently used solvents, but it should be noted that prolonged contact (>2 weeks) of the azide ion with dichloromethane can produce highly explosive products [8, 9] dibromomethane produces the explosive bisazidomethane in 60% yield after 16 days [8]. 

Sodium azide is not as sensitive as lead azide or silver azide to friction or mechanical shock. Since sodium azide reacts with metal oxides to generate nitrogen gas, mixtures of sodium azide and metal oxides are used as pyrolants in gas generators. However, sodium azide reacts with copper and silver to form the corresponding azides, both of which are detonable pyrolants. 

Junjappa and co-workers (9) reported the cycloaddition of sodium azide to the polarized ketene-(5,5)-acetal 33 to give the tiiazole 35 they also reported an intermolecular cycloaddition of tosyl azide 37 with the enamine 36 to give an unstable triazoline intermediate 38. Ring opening 38 followed by a Dimroth rearrangement afforded the triazole 41 (Scheme 9.9). 

A general synthesis of functionalized 1,2,3-triazolyl acylsilanes (160) was based on the intermolecular cycloaddition of azides 159 with the alkynyl acylsilane 158 (Scheme 9.32) (32). The resulting triazolyl acylsilanes (160) were smoothly converted into their corresponding aldehydes 161 upon treatment with sodium hydroxide in ethanol. 

Sodium azide reacts with various epoxides at 25°-30°C at pH 6-7 to give azido alcohols [57-59]. The use of harsh conditions as earlier employed by Van der Werf et al. [59] (16-40 hr reflux in dioxane) led to the production of 1,3-diazidopropanol instead of l-azido-3-chloro-2-propanol when starting with epichlorohydrin. Several representative examples of the conditions and products of the reaction of azides with epoxides are shown in Table V. 

PBS containing 0 1 % (w/v) sodium azide. Sodium azide is toxic by ingestion and inhalation, and should be handled with gloves m a fume hood... 

Alkyl azides. Sodium azide as such is of little use for preparation of alkyl azides by nucleophilic substitution reactions because of solubility problems. The reaction can be carried out under phase-transfer conditions with methyltrioctylam-monium chloride/NaN3.3 An even more effective polymeric reagent can be obtained by reaction of NaN3 with Amberlite IR-400.4 This reagent converts alkyl bromides, iodides, or tosylates into azides at 20° in essentially quantitative yield. The solvents of choice are CH3CN, CHC13, ether, or DMF. 

Soluble azides react with iron (III) salt solutions to produce a red color, similar to that of iron(lll) thiocyanate. Sodium azide is not explosive, even on percussion, and nitrogen may be evolved upon heating. Widi iodine dissolved in cold ether, silver azide forms iodine azide (INj), a yellow explosive solid. 

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