Hydroxylamine Azide

This compound, (NH30H)N3, is made by neutralizing hydroxylamine with hydrazoic acid and is described as a white, volatile solid which is water soluble and melts at 66°C [192]. 

---

The reaction of nitroalkanes and dinitroalkanes with sodium hydrogen telluride gives nitrosoalkane dimers and olefins, respectively.96 The reduction of other nitrogenated species such as hydroxylamines, azides, nitroso, azo, and azoxy compounds can also be performed by using tellurium reagents.6,11,12... 

Schweiger and Buckel (2J2) have investigated the conversion of (/ )-lactate to propionate by cell-free extracts of C. propionicum. Very low levels of acrylate were detected [0.5% of the (R)-lactate present], which suggests that acrylate is an intermediate in the conversion. This is consistent with their observation of HTO formation utilizing [3- H]lactate as substrate (233). Furthermore, the inhibition of (R)-lactate dehydration by hydroxylamine, azide, and 2,4-dinitrophenol is analogous to the inhibition of 2-hydroxyglutarate by these compounds (229), and was suggested to be indicative of a radical mechanism (232). 

Nitrogen, phosphorus and arsenic form more than one hydride. Nitrogen forms several but of these only ammonia, NHj, hydrazine, N2H4 and hydrogen azide N3H (and the ammonia derivative hydroxylamine) will be considered. Phosphorus and arsenic form the hydrides diphosphane P2H4 and diarsane AS2H4 respectively, but both of these hydrides are very unstable. 

Mn04 Reduction with arsenate(III), ascorbic acid, azide, hydrazine, hydroxylamine, oxalic... 

Diphenylthiirene 1-oxide reacts with hydroxylamine to give the oxime of benzyl phenyl ketone (79JA390). The reaction probably occurs by addition to the carbon-carbon double bond followed by loss of sulfur monoxide (Scheme 80). Dimethylamine adds to the double bond of 2,3-diphenylthiirene 1,1-dioxide with loss of sulfur dioxide (Scheme 81) (75JOC3189). Azide ion gives seven products, one of which involves cleavage of the carbon-carbon bond of an intermediate cycloadduct (Scheme 81) (80JOC2604). 

Nucleophiles like alcohols [2, S], hydrogen sulfide [2], thiols [2,10], ammonia, amines, hydrazines, hydroxylamines [2 11, 12, 13, 14, 75], azides [2], other pseudohalides [2], phosphonates [2,16,17,18,19, 20], and phosphanes [2,19] add rapidly across the CO or CN double bond to yield stable adducts The phosphonate adduets undergo a subsequent aleohol—lester rearrangement [19, 20] (equation 2)... 

Nitrogen forms more than 20 binaiy compounds with hydrogen of which ammonia (NH3, p. 420), hydrazine (N2H4, p. 427) and hydrogen azide (N3H, p. 432) are by far the most important. Hydroxylamine, NH2(OH), is closely related in structure and properties to both ammonia, NH2(H), and hydrazine, NH2(NH2) and it will be convenient to discuss this compound in the present section also (p. 431). Several protonated cationic species such as NH4+, N2H5+, etc, and deprotonated anionic species such as NH2 , N2H3 , etc. also exist but ammonium hydride, NH5, is unknown. Among... 

Consistent with this NNO can be made from NH4N03, and N NO from NH4 N03. Alternative preparative routes (Fig. 11.9) are the reduction of aqueous nitrous acid with either hydroxylamine or hydrogen azide ... 

Reductive alkylations have been carried out successfully with compounds that are not carbonyls or amines, but which are transformed during the hydrogenation to suitable functions. Azides, azo, hydrazo, nitro and nitroso compounds, oximes, pyridines, and hydroxylamines serve as amines phenols, acetals, ketals, or hydrazones serve as carbonyls 6,7,8,9,12,17,24,41,42,58). Alkylations using masked functions have been successful at times when use of unmasked functions have failed (2). In a synthesis leading to methoxatin, a key... 

Lustrous yel needles, mp 33° (Refs 2 3), prepd by the action of hydroxylamine (yield 50%), hydrazine (yield 20%), or Na azide on 2-naphtha-lenediazonium sulfate (Ref 3) or by the action of hydroxylamine sulfate on 2-naphthalene diazonium sulfate in sulfuric acid/glac acet ac (Ref 5)... 

The reaction of arenediazonium ions with hydroxylamine is known, but has been little investigated (Gattermann and Ebert, 1916). The l-aryl-3-hydroxytriazene (6.23) formed initially is in most cases unstable (except if Ar = anthraquinonyl). Under alkaline conditions elimination of N20 yields the amine, whereas the aryl azide is formed in the presence of acid (Scheme 6-15). There are, however, better methods for the synthesis of aryl azides (review Biffin et al., 1971, p. 147). 

Wahrendsich Diazonium-Salze durch Triphenyl-phosphan zu Hydrazinenreduzicrcn lasscn (s.Bd. X/2, S. 218), werden Hydroxylamine durch tert.-Phosphane und Azide durch Triphenyl-phosphan zu Aminen reduziert (s. Bd. X/l, S. 1242 bzw. Bd. X/3, S. 882). Bedeutung zur Herstellung von Aminen haben diese Verfahren nicht. Oxaziridine werden durch Triphenyl-phosphan zu lminen reduziert (s.Bd. X/4, S. 468). 

Organoboranes react with a mixture of aqueous NH3 and NaOCl to produce primary amines. It is likely that the actual reagent is chloramine NH2CI. Chloramine itself,hydroxylamine-O-sulfonic acid in diglyme, and trimethyl-silyl azide " also give the reaction. Since the boranes can be prepared by the hydroboration of alkenes (15-16), this is an indirect method for the addition of NH3 to a double bond with anti-Markovnikov orientation. Secondary amines can be prepared by the treatment of alkyl- or aryldichloroboranes or dialkylchlorobor-anes with alkyl or aryl azides. 

It reacts violently when it is heated with aluminium. It causes hydrogen sulphide to combust. It decomposes hydroxylamine chiorohydrate, hydrogen peroxide (detonation) and potassium azide violently. 

Use of nitrous acid to liberate a free keto-acid from its semicarbazone caused formation of hydrogen azide which was co-extracted into ether with the product. Addition of silver nitrate to precipitate the silver salt of the acid also precipitated silver azide, which later exploded on scraping from a sintered disc. The possibility of formation of free hydrogen azide from interaction of nitrous acid and hydrazine or hydroxylamine derivatives is stressed. 

Bajic and Jaselskis [153] described a spectrophotometric method for the determination of nitrate and nitrite in seawater. It included the reduction of nitrate and nitrite to hydroxylamine by the zinc amalgam reactor (Jones reductor) at pH 3.4 and reoxidation of the product with iron (III) in the presence of ferrozine. Interference by high levels of nitrite could be eliminated with azide treatment. Levels of nitrate of 0.1 mg/1 could be detected with a precision of 3% in the presence of large amounts of nitrite and chloride. 

Lead(II) azide Lead chromate Lead dioxide Calcium stearate, copper, zinc, brass, carbon disulfide Iron hexacyanoferrate(4-) Aluminum carbide, hydrogen peroxide, hydrogen sulfide, hydroxylamine, ni-troalkanes, nitrogen compounds, nonmetal halides, peroxoformic acid, phosphorus, phosphorus trichloride, potassium, sulfur, sulfur dioxide, sulfides,... 

The aryl azides are very reactive compounds. By the action of acids, for example, they lose the two terminal N-atoms as N2 the residual C8H5N< combines with water to form aryl hydroxylamine, but this at once undergoes rearrangement and becomes an aminophenol. 

---