Ferrous Azide

T. Curtius and J. Rissom showed that the evaporation of a soln. of manganese carbonate in hydrazoic acid gives a pulverulent, non-crystalline manganese hydroxyazide, Mn(OH)(N3)2, which cannot be purified by re-crystallization. The product is sparingly soluble in water it does not explode by percussion, but does so on a hot plate. L. Wohler and F. Martin gave 203° for the explosion temp, of manganese azide. T. Curtius and J. Rissom obtained a colourless soln. of ferrous azide by the action of sodium azide on a soln. of ferrous ammonium sulphate when boiled, the salt decomposes and when shaken in air, a blood-red soln. of ferric azide is formed. The same salt can also be obtained directly from ferric salts. When the soln. of ferric azide is boiled, ferric hydroxide is precipitated and, added T. Curtius and A. Darapsky, if allowed to stand in... 

Earlier, Turrentine (Ref 4) obtained ferric azide in soln by electrolysis of a dil sodium azide soln using iron electrodes and later by Browne et al (Ref 6) on using iron electrodes in liq amm solns of ammonium azide, but the product was ammonolyzed to an Ammono-Basic Ferric Azide. Curtius et al (Refs 1 2), with ferric alum and NaN, obtained ferric azide in soln and they also repotted that iron dissolved in dil aq hydrazoic acid to form the azide, but the soln decompd on evapn giving either the basic azide or hydroxide. In 1934 Franklin (Ref 9) noted that aq hydrazoic acid reacts on iron to form ferric azide, nitrogen and ammonia together with a small amt of hydrazine. According to Franklin Ferrous Azide, Fe(Nj), is formed first and oxidizes to ferric azide when the soln is warmed with excess hydrazoic acid present. Ricca (Ref 11) studied the reactions of the ferric ion with hydrazoic acid on electrolysis of their solns and obtained results which would indicate that ferric azide has the structure [Fe(Nj)](Nj)2... 

The iron from the capsule experiments was brittle and fell apart when rubbed. In this investigation iron azide (ferric or ferrous azide) and hydrazine could not be detected, contrary to the work of Franklin [51] and Curtius and Risson [52]. Polyethylene becomes brittle, opaque, and porous when exposed to hydrazoic acid, and hydrazoic acid diffused through 0.008 in polyethylene bags within 90 days. Blay and Dunstan [53] reported little azide interaction with polyethylene, but noted a marked drop in azide value when Service lead azide was in contact with various rubbers, plastics, and other synthetic packaging materials. A reduction in azide content as high as 70% was shown (Figure 4). This was attributed to the slow release of carbon dioxide from the test material, followed by further hydrolysis of the lead azide. 

Treatment of alkenes with sodium azide, ferrous ion, and hydrogen... 

Ferrous chloride-hydrochloric acid mixtures catalyzed the thermal decomposition of sulphonyl azides in isopropyl alcohol to give occasionally almost quantitative yields of sulphonamide and acetone, and the molar ratio of azide consumed to ferric chloride formed was typically of the order of 20 to 1 21>. 

The products are isolated in good yield in a one-stage synthesis from starting materials that are readily available in the main. An alternative method involves the decomposition of the corresponding azides.9,12 These compounds are less readily available and are more hazardous to use than are the nitro compounds used in the present synthesis. This synthesis also gives better yields than the cyclization using ferrous oxalate, 2,13 which is performed under much harsher conditions. 

The donor type D5 comprises the two species azide and hydroxy-lamine. These both react with the enz5mie in the presence of peroxide to give rise to ferrous forms of catalase, otherwise normally inaccessible (catalase is the only common hemoprotein that is nonreducible by dithionite). The final inhibited form of catalase in the presence of azide and peroxide is NO-ferrocatalase, but not every azide molecule becomes an NO only in the presence of CO is there a stoichiometric inhibition of enzyme by peroxide with formation of 1 equiv of CO-ferrocatalase for every peroxide molecule added (43). This suggested a three-electron reduction of compound I either to give ferrocatalase, N2, and NO (10-20% total) or to give ferrocatalase, N, and N2O (80-90% total). However, Kalyanaraman et al. (45) have demonstrated the formation of the azidyl (N=N=N ) radical in the reaction, and Lardinois... 

Both classical type A enzymes (clade III) and the heme d family (clade II) show a comparatively high sensitivity to azide inhibition and are reduced to ferrous forms in the presence of peroxide and azide (47). In contrast, the catalase-peroxidase (type B) enzymes (see below) are only weakly azide-sensitive. 

This mechanism can be illustrated by the reaction of ferrous ions with hydrogen peroxide (42), the reduction of organic peroxides by cuprous ions (63), as well as by the reduction of perchlorate ions by Ti(III) (35), V(II) (58), Eu(II) (71), The oxidation of chromous ions by bromate and nitrate ions may also be classified in this category. In the latter cases, an oxygen transfer from the ligand to the metal ion has been demonstrated (8), As analogous cases one may cite the oxidation of Cr(H20)6+2 by azide ions (15) (where it has been demonstrated that the Cr—N bond is partially retained after oxidation), and the oxidation of Cr(H20)6+2 by 0-iodo-benzoic acid (6, 8), where an iodine transfer was shown to take place. 

Determination of Azide as NaNt. Pipette a 25 ml portion of the sample into a 500 ml Erin flask and dil with w to 150-200 ml. Titrate with 40% sulfuric acid to just fo the phpht end-point, not overrunning it. Add N/10 ceric sulfate soln in 5 ml portions until the soln becomes deep yel, indicating an excess of ceric sulfate. Record the exact amt used. Add 10 ml of 40% sulfuric acid and 2 drops of o-phenanthroline indicator (prepd by dissolving 14.85 g of o-phenanthroline monohydrate, CiaHsNa HaO in 1 1 of 0.025 M freshly prepd ferrous sulfate... 

Ferric potassium sulfate 1 A156—A157 Ferric triazide see Ferric azide 1 AS43 Ferricyanides 6 F15 Ferri-ferrous oxide 6 FI 5 Ferrifracteur 6 Fi5 Ferrite 6 FI 5... 

Ferric Azide A543-L Ferric Azide, Basic A543-R Ferric Triazide. See Iron Azide A543-L Ferrous Acetylide. See Iron Acetylide A76-R... 

---