Hydroxylamine-O-sulfonic acid

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Hydroxylamine-O-sulfonic acid

  Oxygen, O
  Nitrogen, N
  Sulfur, S
  Hydrogen, H
Names
Other names
Aminosulfuric acid
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.019.065 Edit this at Wikidata
EC Number
  • 220-971-6
  • InChI=1S/H3NO4S/c1-5-6(2,3)4/h1H2,(H,2,3,4)
    Key: DQPBABKTKYNPMH-UHFFFAOYSA-N
  • NOS(=O)(=O)O
Properties
H3NO4S
Molar mass 113.09
Appearance white solid
Melting point 210 °C
cold water
Acidity (pKa) 1.48[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Hydroxylamine-O-sulfonic acid (HOSA) or aminosulfuric acid is the

condensed structural formula H2NOSO3H, though it actually exists as a zwitterion[3] and thus is more accurately represented as +H3NOSO3−. It is used as a reagent for the introduction of amine groups (–NH2), for the conversion of aldehydes into nitriles and alicyclic ketones into lactams (cyclic amides), and for the synthesis of variety of nitrogen-containing heterocycles.[3][4][5]

Preparation

According to a laboratory procedure

hydroxylamine sulfate with fuming sulfuric acid (oleum). The industrial process is similar.[6]

(NH3OH)2SO4 + 2SO3 → 2H2NOSO3H + H2SO4

The sulfonation of hydroxylamine can also be effected with

chlorosulfonic acid[3] by a method first published in 1925[7] and refined for Organic Syntheses.[8]

The hydroxylamine-O-sulfonic acid, which should be stored at 0 °C to prevent decomposition, can be checked by iodometric titration.[9]

Structure

Analogous to sulfamic acid (H3N+SO3−) and as is the case generally for amino acids, HOSA exists in the solid state as a zwitterion: H3N+OSO3−. It resembles an ammonia molecule coordinate covalently bonded to a sulfate group.[10]

Reactions

HOSA reacts under basic conditions as an electrophile and under neutral and acid conditions as a nucleophile.[4][11]

Reaktivität of Hydroxylamine-O-sulfonsäure als Elektrophil und als Nukleophil
Reaktivität of Hydroxylamine-O-sulfonsäure als Elektrophil und als Nukleophil

Aminations

Synthesis of N-Aminopiperidin with HOSA
Synthesis of N-Aminopiperidin with HOSA

It reacts with tertiary amines to trisubstituted hydrazinium salts and with pyridine to the 1-amino pyridinium salt.[12]

Synthesis of 1-Aminopyridin with HOSA
Synthesis of 1-Aminopyridin with HOSA

From 1-aminopyridinium salts the photochemically active 1-N-iminopyridinium ylides are accessible by acylation.[13] The photochemical rearrangement of the obtained 1-N-iminipyridinium ylides leads in high yields to 1H-1,2-diazepines[14]

Synthesis of 1,2-Diazepinen aus Iminopyridiniumyliden
Synthesis of 1,2-Diazepinen aus Iminopyridiniumyliden

N-amination of

dimerizes to biphenylene in good yields.[15]

Synthesis of Benzyne and Biphenylene from 1-Aminobenzotriazole
Synthesis of Benzyne and Biphenylene from 1-Aminobenzotriazole

Electron deficient heterocycles, such as tetrazole, can be N-aminated with hydroxylamine-O-sulfonic acid, while even more electron-deficient compounds, such as 5-nitrotetrazole, react only with stronger aminating agents such as O-tosylhydroxylamine or O- mesitylene sulfonylhydroxylamine to amino compounds, which were investigated as explosives.[16]

1-Aminotetrazol und 2-Aminotetrazol durch Aminierung of Tetrazol with HOSA
1-Aminotetrazol und 2-Aminotetrazol durch Aminierung of Tetrazol with HOSA

In the N-amination of the unsubstituted tetrazole, a mixture of 1-amino- and 2-aminotetrazole is obtained.

Synthesis of Sulfiminen with HOSA
Synthesis of Sulfiminen with HOSA

Also

phosphorus compounds (such as triphenylphosphine) can be aminated to phosphine imides via the intermediate aminotriphenylphosphonium hydrogen sulfate.[17]

The reaction of hydroxylamine-O-sulfonic acid with metal salts of sulfinic acids in sodium acetate solution produces primary sulfonamides in very good yields.[18]

Synthesis of primären Sulfonamiden aus Sulfinaten
Synthesis of primären Sulfonamiden aus Sulfinaten

Diimine can formed in situ from hydroxylamine-O-sulfonic acid respectively hydroxylamine-O-sulfonic acid hydroxylamine sulfate mixtures, which hydrogenates selectively conjugated multiple bonds.[20]

With carbonyl compounds

At room temperature and below, hydroxylamine-O-sulfonic acid reacts with ketones and aldehydes as a nucleophile to the corresponding oxime-O-sulfonic acids or their salts.[19] The oxime-O-sulfonic acids of aldehydes react above room temperature upon elimination of sulfuric acid in high yields to nitriles.[20]

Reaktion of HOSA with Carbonylverbindungen
Reaktion of HOSA with Carbonylverbindungen

Aliphatic ketones provide under similar conditions in very high yields oximes, arylalkyl ketones react in a Beckmann rearrangement to amides. When heated to reflux for several hours under acidic conditions (e.g., in the presence of concentrated formic acid) alicyclic ketones react to provide lactams in high yields.[21]

2-Azacyclooctanon durch Reaktion of Cycloheptanon with HOSA
2-Azacyclooctanon durch Reaktion of Cycloheptanon with HOSA

Under basic conditions in the presence of primary amines, hydroxylamine-O-sulfonic acid forms with aldehydes and ketones (e.g. cyclohexanone[22]) diaziridines, which can easily be oxidized to the more stable diazirines.

3,3-Pentamethylendiaziridin durch Reaktion of Cyclohexanon mit HOSA
3,3-Pentamethylendiaziridin durch Reaktion of Cyclohexanon mit HOSA

The reaction also provides substituted aziridines from simple aldehydes and ketones with high yield and diastereoselectivity.[23]

Synthesis of Diaziridinen with HOSA
Synthesis of Diaziridinen with HOSA

1,2-Benzisoxazole is efficiently produced by nucleophilic attack of hydroxylamine-O-sulfonic acid to the carbonyl group of 2-hydroxybenzaldehyde followed by cyclization.[24]

Synthesis of 1,2-Benzisoxazol aus Salicylaldehyd und HOSA
Synthesis of 1,2-Benzisoxazol aus Salicylaldehyd und HOSA

1,2-Benzisoxazole is a structural element in the antipsychotic risperidone and paliperidone, as well as the anticonvulsant zonisamide.

In a

one-pot reaction, N-aryl[3,4-d]pyrazolopyrimidines are obtained in good yields from simple 4,6-dichloropyrimidine-5-carboxaldehyde,[25]

N-Aryl-Pyrazolopyrimidine
N-Aryl-Pyrazolopyrimidine

which can be used as purine analogs for a wide range of diagnostic and therapeutic applications.[26]

Further reactions

The chemiluminescence of the system luminol/cobalt(II) chloride is dramatically enhanced by the addition of hydroxylamine-O-sulfonic acid.[27]

References

  1. LCCN 82-16524
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  2. ^
    ISBN 9780470132364. {{cite book}}: |journal= ignored (help
    )
  3. ^
    ISBN 978-0-12-352651-9
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  4. ^ a b Wallace, Raymond G. (1980). "Hydroxylamine-O-sulfonic acid – a versatile synthetic reagent". Aldrichimica Acta. 13 (1): 3–11.
  5. ISBN 978-3-13-172181-5
    .
  6. ^ US patent 3281209, Wehrmeister, Herbert L. & Yalowitz, Harold I., "Process for the preparation of hydroxylamine-O-sulfonic acid", published 1966-10-25, issued 1966-10-25, assigned to Commercial Solvents Corporation 
  7. doi:10.1002/zaac.19251470115
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  8. doi:10.15227/orgsyn.058.0032
    ; Collected Volumes, vol. 6, p. 943.
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  10. doi:10.1021/ic50049a017
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  11. ISBN 978-0-471-93623-7
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  12. doi:10.15227/orgsyn.043.0001
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  13. ^ J. Streith (1991). "The Photochemistry of N-Iminopyridinium Ylides in Retrospect. From a Simple Concept to Some Applications". CHIMIA (in German). 45 (3): 65–76.
  14. doi:10.1351/pac197749030305
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  15. doi:10.1039/J39690000742
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  16. PMID 22751656
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  17. doi:10.1002/jlac.19586180107
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  18. doi:10.1055/s-1986-31862
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  19. doi:10.1016/S0040-4039(01)83223-8
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  20. doi:10.1016/S0040-4039(01)91857-X
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  21. doi:10.15227/orgsyn.063.0188
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  22. doi:10.15227/orgsyn.045.0083
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  23. PMID 26216745
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  24. doi:10.1016/S0040-4020(01)96921-2
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  25. PMID 22734502
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  26. doi:10.1055/s-0033-1338862
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  27. PMID 25766485
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