Hydroxylamine 2-sulfonic acid

Sodium hypnnitrite Na N 0 is formed (I) by reaction of sodium nitrate or nitrite solution with sodium amalgam (sodium dissolved in incrcuryl, alter which acetic acid is added to neutralize the alkali. Sodium stannite ferrous hydroxide, or electrolytic reduction w ith mercury cathode may also be utilized. (2) by reaclion of hydroxylamine sulfonic acid and sodium hydroxide. Silver hyponitrite is formed by reaclion of silver nitrate solution and sodium hyponitrite. 

A(-Nitrosation of oximes by nitrosyl halides or nitrite esters often results in the formation of A(-nitrimines, R R C=NN02, these compounds being formed by rearrangement of the initial adducts. A(-Amination of oximes by chloramine or by hydroxylamine-< -sulfonic acid can result in the formation of diazo compounds (Scheme 28). The reaction, known as the Forster reaction, has been used for the preparation of aryldiazoalkanes, although better methods are usually available. Diazo ketones of the general formula (49) have also been prepared by this method from the oximes. ... 

Hydroxylamine sulfonic acid, hydroxylamine and catalytic amounts of trifluoromethanesulfonic acid, or 0-mesitylenesulfonylhydroxylamine converts ketones directly to the lactams under mild conditions (reflux in formic acid). 

Additions to multiple bonds catalyzed by radical initiators produce novel synthetic methods. Carboxylic acids add to acetylenic compounds in the presence of organic peroxides. Acetic acid and acetylene yield adipic acid 1-hexyne and acetic acid give octen-3-oic acid. Radical amination of olefins with hydroxylamine sulfonic acid and hydroxylamine in the presence of FeCla gives the corresponding l-amino-2-chloro compounds. ... 

Direct amination of quinoxalinones with hydroxylamine-( -sulfonic acid produces the 1-amino derivatives (135) in 70-80% yield, and subsequent oxidation with lead tetraacetate gives the 1,2,4-benzotriazines (138). Benzotriazine formation probably involves the formation of an intermediate nitrene (136), ring expansion to a benzo-triazepinone (137) and subsequent loss of carbon monoxide. The nitrene (136 R = Ph) was trapped as the sulfoximide 139 when the oxidation was carried out in the presence of dimethyl sulfoxide. ... 

Aminobenzopyrazole. Amination of benzop)irazole using hydroxylamine sulfonic acid in the presence of sodium hydroxide delivers a mixture of 1-amino- and 2-aminoindazoles in 50 and 33% isolated yields (eq 19). ... 

Other Applications. Hydroxylamine-O-sulfonic acid [2950-43-8] h.2is many applications in the area of organic synthesis. The use of this material for organic transformations has been thoroughly reviewed (125,126). The preparation of the acid involves the reaction of hydroxjlamine [5470-11-1] with oleum in the presence of ammonium sulfate [7783-20-2] (127). The acid has found appHcation in the preparation of hydra2ines from amines, aUphatic amines from activated methylene compounds, aromatic amines from activated aromatic compounds, amides from esters, and oximes. It is also an important reagent in reductive deamination and specialty nitrile production. 

Appropriate pyrido[2,3-d]pyrimidin-5-ones with formyl groups in the 6-position have been oxiized to piromidic (68) and pipemidic (69) acids, or to intermediates for these, using moist silver oxide, chromium trioxide (potassium dichromate), potassium permanganate or, alternatively, sodium chlorite/hydroxylamine-O-sulfonic acid. 6-Acetyl groups have been similarly oxidized using sodium hypobromite in aqueous dioxane, whilst 2-acetyl groups give dimethylaminomethylene derivatives en route to 2-pyrazolylpyrido[2,3-d]pyrimidines. 

Amination at an azole ring nitrogen is known for Af-unsubstituted azoles. Thus 4,5-diphenyl-1,2,3-triazole with hydroxylamine-O-sulfonic acid gives approximately equal amounts of the 1- (104) and 2-amino derivatives (105) (74AHC(16)33). Pyrazole affords (106) and indazole gives comparable amounts of the 1- and 2-amino derivatives. 

The powerful aminating agents hydroxylamine O-sulfonic acid and O-mesitylenesulfonyl-hydroxylamine have been used to prepare compounds (270)-(274) (80JCR(M)0514,76CPB2267). 

N-Amination of indazole affords a mixture of 60% (271) and 40% (272), which compares with the 55 45 ratio obtained in methylation (Section 4.04.2.1.3(viii)). A camphopyrazole derivative (a mixture of tautomers 275 and 276) when treated with hydroxylamine O-sulfonic acid yields exclusively the (4S,7i )-4,7-methano-2-amino-7,8,8-trimethyl-4,5,6,7-tetrahydro-2H-indazole (277) (79YZ699). 

The treatment of 2-hydroxyacetophenone with hydroxylamine-O-sulfonic acid in dilute aqueous base produced 3-methyl-1,2-benzisoxazole. The mechanism was reported to be a C(2)—C(3) ring closure via intermediate (560) (Scheme 171). Salicylaldehyde failed to cyclize with dilute base, but with 20% KOH and hydroxylamine-O-sulfonic acid the transformation to 1,2-benzisoxazole succeeded (76MI41600). Kemp and Woodward isolated an oxime sulfonate (561) from salicylaldehyde and hydroxylamine-O-sulfonic acid and the subsequent decomposition gave 1,2-benzisoxazole in 95% yield (65T3019). 

Trichloromethyloxaziridine (98) transfers its NH group to primary amines under the conditions of its formation from hydroxylamine-O-sulfonic acid. Thus the slow... 

Compound (253) is formed from benzaldehyde and methylhydroxylamine-O-sulfonic acid in 35% yield. With ethyl-substituted chloramine or hydroxylamine-O-sulfonic acid yields do not exceed 10%, which is assumed to be due to steric hindrance and is foreseeable for both carbonyl addition and O —N bond formation. 

Two substituents on two N atoms increase the number of diaziridine structures as compared with oxaziridines, while some limitations as to the nature of substituents on N and C decrease it. Favored starting materials are formaldehyde, aliphatic aldehydes and ketones, together with ammonia and simple aliphatic amines. Aromatic amines do not react. Suitable aminating agents are chloramine, N-chloroalkylamines, hydroxylamine-O-sulfonic acid and their simple alkyl derivatives, but also oxaziridines unsubstituted at nitrogen. Combination of a carbonyl compound, an amine and an aminating agent leads to the standard procedures of diaziridine synthesis. 

This reaction provides a wide variety of products since decomposition of the deuterated alkylborane intermediate (164) can be achieved with hydrogen peroxide to yield labeled alcohols (165), with hydroxylamine-O-sulfonic acid leading to deuterated amines (166), as well as with boiling propionic acid or propionic acid-OD, to form mono- (167) or dideuterio (168) hydrocarbons, respectively. Furthermore, if a monodeuterium label at the sterically more accessible position (170) is sufficient, the use of expensive metal deute-... 

The major development in the Knorr pyrrole synthesis has been access to the amine component. For example, use of preformed diethyl aminomalonate with 1,3-diketones affords much higher yields of pyrroles 14. Reaction of 6-dicarbonyl compounds with hydroxylamine 0-sulfonic acid gives pyrroles 15 in one step. Weinreb a-aminoamides have found use in the Knorr pyrrole synthesis of a wide variety of pyrroles 16. °... 

The hydroxy group of furazan 263 reacted with cyanogen bromide in glyme in the presence of Li2C03 to give cyanate 264 in 70-85% yield (97MI8). Upon treatment with Mc4NN3 and subsequently with a basic solution of hydroxylamine-0-sulfonic acid, /V-aminotetrazole 265 was obtained in 35% yield (Scheme 171). 

Isotellurazoles la-e were first prepared by coupling ethynyl ketones with hydroxylamine-O-sulfonic acid and K2Te in aqueous solution of sodium acetate... 

Reaction of hydroxylamine-0-sulfonic acid with cyclohexanone in alkaline solution can be shown to give pentamethyleneoxazirane (16). Compound 16 is an isomer of cyclohexanone oxime. It decomposes even at room temperature and thus cannot be prepared in a pure state. 

Thus the structure of the oxazirane must formally involve elimination of water from one molecule each of the carbonyl compound and of an alkyl hydroxylamine. (In the synthesis of oxazirane from N-methylhydroxylamine-O-sulfonic acid and benzaldehyde, this method... 

A simple chemical proof of structure of the diaziridines is given by the synthesis of the same diaziridine 42 from cyclohexanone either using methylamine and hydroxylamine-O-sulfonic acid or using ammonia and methylhydroxylamine-O-sulfonic acid. ... 

N-Aminobenzoxazolin-2-one (4), which was readily prepared by animation of benzoxazolin-2-one with hydroxylamine-O-sulfonic acid, is also a useful nitrene precursor (Scheme 2.2). Oxidation of 4 with lead(iv) acetate in the presence of a conjugated diene resulted in exclusive 1,2-addition of nitrene 5, to yield vinylazir-idine (6) in 71 % yield [6]. The formation of vinylaziridines through 1,2-additions of methoxycarbonylnitrene (2) or amino nitrene 5 contrasts with the claimed 1,4-ad-dition of nitrene itself to butadiene [7]. Since the reaction proceeded stereospecif-ically even at high dilution, the nitrene 5 appears to be generated in a resonance-stabilized singlet state, which is probably the ground state [8]. 

Because aqueous solutions of hydroxylamine-O-sulfonic acid are not very stable, it is very important to use freshly prepared solutions. The purity of hydroxylamine-O-sulfonic acid should be checked by iodometric titration. If it is less than 85-... 

Hydrazine hydrate, in preparation of sulfonylhydrazides, 40, 93, OS in reduction of 2-nitrofiuorene to 2-aminofluorene, 40, 5 in Wolff-Kishner reduction, 43, 34 Hydrazines, asymmetrically substituted by N-aminatiou of amines by hydroxylamine-O-sulfonic acid, 43,2... 

Hydroxylamine-O-sulfonic acid for N-amination of pyridine, 43, 1 Hydroxylation of indene, 41, 53 2-Hydroxy-3-methylbenzoic add, oxidation to 2-hydroxyisophthalic acid by lead dioxide, 40, 48 Rydroxymethyleerrocene. 40, 52... 

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. 

In a similar reaction, aromatic acyl halides are converted to amines in one laboratory step by treatment with hydroxylamine-O-sulfonic acid. " ... 

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