Hydroxylamine ammonium salts Hydroxylamines

Amine oxides 2, which can be prepared by oxidation of amines 1, react upon heating to yield an olefin 3 and a hydroxylamine 4. This reaction is called the Cope elimination reaction,and as a synthetic method is a valuable alternative to the Hofmann degradation reaction of quaternary ammonium salts. 

Hydroxylamine, IV-benzoyl-lV-phenyl-in gravimetry, 1, 532 liquid-liquid extraction, 1, 544 Hydroxylamine, A -cinnamoyl-A -phenyl-liquid-liquid extraction, 1,544 Hydroxylamine, Ar,A -di-(-butyl-metal complexes, 2, 798 Hydroxylamine, Ay/V-diethyl-metal complexes, 2,798 Hydroxylamine, AAmethyl-metal complexes, 2,798 Hydroxylamine, A -2-naphthol-A -nitroso-ammonium salt — see Ncocupferron Hydroxylamine, A -nilrosophenyl-ammonium salt — see Cupferron Hydroxylamine ligands, 2, 101 Hydroxylamine oxido reductase, 6, 727 Hydroxylases molybdenum, 6,658,662 Hydroxylation arenes... 

Other nitrogen compounds, among them hydroxylamine, hydrazines, and amides (15-9), also add to alkenes. Even with amines, basic catalysts are sometimes used, so that RNH or R2N is the actual nucleophile. Tertiary amines (except those that are too bulky) add to Michael-type substrates in a reaction that is catalyzed by acids like HCl or HNO3 to give the corresponding quaternary ammonium salts. " ... 

The situation does not improve with mixtures with the hydrides of the elements. Thus, a detonation occurred during contact between water and chlorine due to an accidental spark. Phosphine, silane and diborane all combust spontaneously in chlorine (their behaviour is the same in oxygen). With hydrogenated nitrogenous compounds ammonia, hydrazine, hydroxylamine, ammonium salts (especially ammonium chloride), and also sulphamic acid (these last two in an acid medium) there is ignition or even detonation. 

If hydroxylamine hydrochloride and sodium nitrite, of normal laboratory particle size, are swiftly shaken together and left to stand, a vigorous gas evolving reaction will start after a short induction period. This is a rare example of spontaneous reaction of solids See Ammonium salts, above... 

De Bruin and van der Plas (79) also used hydroxylamine in an attempt to identify carbonyl groups. It is not stated whether this reagent was used as free base or as a salt. The considerable nitrogen uptake was very nearly the same as on reaction with ammonia in methanol. Perhaps ammonium salts had been formed in both reactions. The same authors found a pronounced reduction with TiClj which exceeded by far the extent of all other reactions. The TiClj reaction gave easily reproducible results. 

Ammonia or an amine can also be introduced between a terminal aldehyde or a ketone and a suitably placed double or triple bond, although the method is of limited use. A poor yield of 4-picoline is obtained when the aldehyde (262) is treated with ammonia or an ammonium salt (49JCS1430) and dihydroquinolines from the phenylethyl ketones (263) and hydroxylamine (76MI20800). More commonly, cyclization occurs by insertion of ammonia, amines or hydroxylamine between two triple or double bonds in the former case, pyrid-4-ones (264) are obtained (54BSF734) in the latter, a piperid-4-one (265) results (1897CB231). Amines have also been used to give N -substituted piperid-4-ones (70OMR(2)197>. In these cases a double 1,4-addition must be involved in the cyclization of the unsaturated nitrile... 

Nitroso-/ -phenylhydroxylamine, of which cupferron is the ammonium salt, has been made by the action of sodium nitrite and hydrochloric acid on /3-phenylhydroxylamine,1 of hydrogen peroxide on normal phenyldiazotates,2 of sodium alcoholate and hydroxylamine on nitrobenzene,3 of nitric oxide on phenyl magnesium bromide,4 and by the action of permonosulfuric acid on aniline in the presence of amyl nitrite.5... 

The hot aq. soln. reacts feebly acid. Dry ammonia gas liberates hydroxylamine, forming ammonium phosphate. The analogous ammonium salt, (NH3)3.H3P04, is difficult to prepare, and the hydroxylamine salt may be constituted ... 

When an excess of nitric acid of 10-50 per cent, strength is treated in the cold with stannous salt soln., hydroxylamine salts are the primary end-product of the reaction, but when the conditions of temp, and cone, are such that the nitric acid and the hydroxylamine salts react, then nitrous oxide is the. chief product together with small amounts of nitHe oxide, nitrogen and traces of nitrogen peroxide. No ammonium salts are formed. When stannous salts are used in excess over the nitric acid, the reaction takes place with hydroxylamine and ammonium salts as the products either in hot or cold soln., but the reaction is very slow in the latter case. When an excess of nitric acid is treated with titanous salt soln., the reaction takes place very rapidly with the formation of nitric oxide as the chief... 

T. Haga did not obtain barium hydroxynitrilo-iso-disulphonate in a state suited for a satisfactory determination of the nature of the salt. The evaporation of a soln. of the ammonium salt with excess of barium hydroxide in a vacuum over sulphuric acid to a small volume removed all ammonia. After removal of the excess of barium hydroxide by carbon dioxide, the filtered soln. was further evaporated in the desiccator. First a viscid and then a bulky, friable, porous mass, devoid of crystalline character, were obtained. The latter was not quantitatively analyzed, but it yielded, when hydrolyzed, barium sulphate and hydroxylamine sulphate in crystals, which were further identified by a very satisfactory acid determination. The product was therefore undoubtedly a barium iso-salt. By using less barium hydroxide, crystallized ammonium barium hydroxynitrilo-iso-disulphonate, 6 (NH4S03)0.NH(NH4S03). Ba(S03)20NH, was formed. 

After the reaction, the solid sodium salt is filtered off and methanol is distilled off under reduced pressure. Hydroxylamine can also be prepared by the ammonolysis of hydroxylammonium salts in liquid ammonia. The ammonium salt precipitates and is filtered off Hydroxylamine is obtained after evaporating the excess ammonia. 

SYNS CUPFERRON N-HYDROXY-N-NITROSO-BENZENAMINE, AMMONIUM SALT KUPFERRON (CZECH) NCI-C03258 N-NITROSOFENYL-HYDROXYLAMIN AMONNY (CZECH) N-NITROSOPHENYLHYDROXYLAMIN AMMONIUM SALZ (GERMAN) N-NITROSOPHENYLHYDRO-XYLAMINE AMMONIUM SALT... 

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