Hydroxylamine-o-sulfonic

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-... 

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

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. " ... 

Cl K2Pt 16921-30-5) see Cisplatin potassium hydrogen phthalate (C H5K04 877-24-7) see Dolasetron mesilate potassium hydroxylamine-O-sulfonate (H2KNO4S 49J59-20- ) see Ibudilast potassium linolate... 

Hydroxylamine, hydrochloride, 55,40 Hydroxylamine sulfate, 58, 32, 36 Hydroxylamine-O-sulfonic acid, 58, 32, 34, 36... 

Reaction of 3-formyM/7-pyrido[ 1,2- ]pyrimidin-l-ones with hydroxylamine O-sulfonic acid at 5 °C, then 50 °C yielded 3-nitriles <2003T4113>. Treatment of 2-hydroxy-3-(dimethylamono)methyF4//-pyrido[l,2- ]pyrimidin-4-one with Mel, then with KCN gave the 3-cyanomethyl derivative <2004MI215>. A condensation product was obtained from 5-amino-l-ethyl-6-hydroxy-l,3-dihydrobenzimidazol-2-one and 3-lbrmyl-2-hydroxyA//-pyndo[ 1,2- ]pynmidin-l-one <2002W002/38549>. l-(2-Aminopyrimidin-4-yl)-8-phenyl-l,2,3,4-tetrahydro-6//-pyrido[l,2- ]pyrimidin-6-ones were prepared from l-(2-methylthiopyrimidin l-yl)-8-phenyl-l,2,3,4-tetrahydro-6//-pyrido[l,2- ]pyrimidin-6-one by treatment with MCPBA, and then with aralkylamines <2005W005/070932>. 

In 1979, Olah [47] reported a one step conversion of alicyclic ketones into lactams by means of hydroxylamine O-sulfonic acid and formic acid under reflux for a few hours. More recently this reaction has been realized under solvent-free conditions with Si02 as inorganic support and focused irradiation, as exemplified in Scheme 8.29 for caprolactam synthesis. 

The reaction of 2-chloro-4,5-dihydroimidazole 347 with hydroxylamine-O-sulfonic acid gives 2-hydroxylamino-4,5-dihydroimidazolium-O-sulfonate 348, which reacts with aldehydes and cyclic ketones to give the imidazo[l,2-f] fused 4,5-dihydro-l,2,4-oxadiazoles 350 (Scheme 58). Mechanistically, the reaction may be explained by the reaction of an imidazoline NH with the carbonyl followed by intramolecular electrophilic amination of the anionic oxygen present in the resultant intermediate 349 and elimination of the sulfate group <2003JOC4791>. 

In another variation of a type E synthesis, thioamides or thioureas condense with /V,/V-dimcthylacylamide dimethyl acetal to give imino compounds which react with amino-transfer reagents like hydroxylamine-O-sulfonic acid and mesitylsulfonyloxyamine (MSH) to give 3,5-substituted-l,2,4-thiadiazoles in excellent yields <1996CHEC-II(4)307>. There have been no new reports of type E syntheses since the publication of CHEC-II(1996). 

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