Hydroxylamine 0-sulfonic acid, synthesis amination

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. 

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. 

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. °... 

Sulfonylhydroxylamines and hydroxylamine O-sulfonic acid have found wide apph-cation in synthesis of amines from achiral or chiral organoboranes and boronate esters and the hydroboration-amination methodology is successfully used for direct amination of alkenes. 0-Sulfonyloximes were also found to be good reagents for synthesis of amines from organomagnesium, -copper and -zinc reagents. 

Following the demonstration of catalytic hydroboration-amination employing hydroxylamine-O-sulfonic acid as the electrophile, extension to the synthesis of secondary amines was considered. 

It is well-known that organoboranes can be utilized to yield primary amines by treating them with chloramine or hydroxylamine-O-sulfonic acid Recently Kabalka et al. reported a convenient synthesis of primary alkyl amines via the reaction of organoboranes with ammonium hydroxide in the presence of sodium hypochlorite (Eq. 13) The reaction presumably proceeds through the in situ formation of chloramine. 

The Schmitz reaction can be unsuccessful in sterically demanding environments in such circumstances, the electrophilic aminating agent reacts faster with ammonia than with hindered ketones <1965JA2665>. Consequently, the synthesis of 2-azi-camphane 64, a compound which is unobtainable under standard conditions <1996TL6647>, was achieved by slow diaziridination of camphor imine hydrochloride 63 (rather than camphor itself) with hydroxylamine-O-sulfonic acid (HOSA)-ammonia, followed by iodine-mediated oxidation (Scheme 22) <2001S379>. 

Knorrpyrrole synthesis. The reagent reacts with some active methylene compiounds to give products of C-amination. Thus 2,4-dimethyl-3,5-dicarhethoxypyrrole (2) can be prepared in one step by the reaction of hydroxylamine-O-sulfonic acid with ethyl acetoacctate (1). ... 

H(55)1759>. N-Unsubstituted l,2-benzisothiazolin-3-ones 344 (R = H R = H, Cl, OMe R = H, Cl, OMe) can be prepared in a chlorine-free synthesis by cyclization of 2-sulfenamoylbenzoates 342 (R = OR, R = NH2) which are prepared by amination of thiosalicylates with hydroxylamine-O-sulfonic acid. N-Substituted sulfenamoylbenzoates, prepared by transamination with different amines, can be cyclized to N-substituted 1,2-benzisothiazolin-3-one 344 (R = PhCH2,/ -MeOC6H4CH2,/>-ClC6H4CH2) <2003H(60)1855>. 

Electrophilic N-aminations have been performed with hydroxylamine-O-sulfonic acid (HOSA)," O-(2,4-dinitrophenyl)hydroxylamine and C>-mesitylenesulfonylhydroxylamine. The use of HOSA is mainly restricted to aqueous reaction media. Imide sodium salts of some heterocycles such as theobromine (88) can be converted to hydrazine derivatives by treatment with 0-(diphenylphosphinyl)hydroxylamine (equation 35)." This reaction has been extended to synthesis of N-arylhyd ines, where R and R are hydrogen, alkyl or aryl (equation 36)." Similarly, trisubstituted hydrazines can be prepared by the use of N-aryl-O-acetylhy oxylamines and secondary amines." A recent publication" concerning the synthesis of l-acyl-2-dkylhydrazines from hydroxamic acids and amines in the presence of activating agents has been found to be erroneous no N—N bond formation occurs under these conditions." ... 

The smooth uptake and transfer of NH groups by carbonyl compounds gives rise to catalytic reaction sequences. In the known synthesis of alkylhy-drazines from amines and hydroxylamine-O-sulfonic acid, added chloral leads to trichloromethyloxaziridine 42, which subsequently transfers its NH-group to the amine." ... 

The majority of diaziridine syntheses proceed by intramolecular electrophilic amination in a geminal compound 84/ ° an aminallike °° compound from an amine, a carbonyl compound, and an electrophilic aminating agent like chloramine or hydroxylamine-O-sulfonic acid. The different ways of diaziridine synthesis differ mainly in the timing of the build-up of this geminal intermediate 84, from which the diaziridine 85 is isolated. 

The readily available 2,3,4,6-fefra-O-benzyl-D-glucopyranose (11) can be used for the synthesis of both nojirimycin (1) and 1-deoxynojirimycin (2) (Schemed).It was treated with EtSH to furnish 12, which was oxidized to the corresponding ketone 13 using TPAP, while the Swern oxidation method failed to produce 13. Treatment of 13 with mercury(ll) salts in the presence of methanol followed by treatment with hydroxylamine hydrochloride in the presence of pyridine afforded the oxime 14 in 73% yield. Treatment of 14 with LiAlH4 in diethyl ether followed by N-protection of the resulting diastereomeric mixture of amines with di-rert-butyl dicarbonate furnished 15 and 16 in 65 and 15% yield, respectively. Pearlman s catalytic hydrogenation of 15 over palladium hydroxide in ethanol followed by treatment of the resulting tetrol with SO2 in water furnished the sulfonic acid 17 in 80% yield. Conversion of 17 into 1 was accomplished by treatment with Dowex 1X2 (OH ) resin. 

The end-product from synthesis of a diaziridine and its fission to alkylhydrazine is the same as is obtained by direct treatment of an amine with chloramine or hydroxylamine-O-sulfonic acid, as the carbonyl component of the Schiff base is recovered however, the detour through the diaziridine is worthwhile because in the direct reaction a considerable excess of the amine must be used to suppress further reaction of the alkylhydrazine product with the animating agent, whereas the diaziridines are unaffected thereby moreover, the diaziridine route is more widely applicable. Even further, the diaziridine route avoids both the requirement for an excess of alkali and the production of the hydrazine as a very dilute aqueous solution, both of which characterize the direct reaction. Indeed it provides an effective and generally applicable synthesis of mono-284,285 and 1,1-dialkyl-hydrazines.286... 

Substituted hydrazines can be prepared by the reaction of amines with chloramine and with hydroxylamine-O-sulfonic acid. Of these two reagents, hydroxylamine-O-sulfonic acid has been introduced more recently and the scope of its reaction is still being explored [IS]. The present authors believe that this is a more convenient reagent than chloramine. By its use, not only mono- but also 1,1-disubstituted hydrazine should be preparable. The synthesis and utilization of N-substituted chloramines and hydroxylamine-O-sulfonic acids require further exploration. 

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