Hydroxylamine-O-sulfonic acid

Last updated
Hydroxylamine-O-sulfonic acid
H3NOSO3.png
HOSAimproved.jpg
   Oxygen, O
   Nitrogen, N
   Sulfur, S
   Hydrogen, H
Names
Other names
Aminosulfuric acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.019.065 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 220-971-6
PubChem CID
  • 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
Appearancewhite 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 inorganic compound with molecular formula H3NO4S that is formed by the sulfonation of hydroxylamine with oleum. [2] It is a white, water-soluble and hygroscopic, solid, commonly represented by 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]

Contents

Preparation

According to a laboratory procedure [2] hydroxylamine-O-sulfonic acid can be prepared by treating 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]

Reaktivitat of Hydroxylamine-O-sulfonsaure als Elektrophil und als Nukleophil Hydroxylamine-O-sulfonsaure Reaktivitat.svg
Reaktivität of Hydroxylamine-O-sulfonsäure als Elektrophil und als Nukleophil

Aminations

Synthesis of N-Aminopiperidin with HOSA N-Aminopiperidin-Synthese.svg
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 1-Aminopyridin-Synthese.svg
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 1,2-Diazepine aus Iminopyridiniumyliden.svg
Synthesis of 1,2-Diazepinen aus Iminopyridiniumyliden

N-amination of 1H-benzotriazole with hydroxylamine-O-sulfonic acid yields a mixture of 1-aminobenzotriazole (major product) and 2-aminobenzotriazole (minor product). From 1-aminotriazole, benzyne is formed in an almost quantitative yield by oxidation with lead(IV) acetate, which rapidly dimerizes to biphenylene in good yields. [15]

Synthesis of Benzyne and Biphenylene from 1-Aminobenzotriazole Dehydrobenzol aus Aminobenztriazol.svg
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 Aminierung von Tetrazol.svg
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 Sulfimine.svg
Synthesis of Sulfiminen with HOSA

Also sulfur compounds (such as thioethers) can be aminated with hydroxylamine-O-sulfonic acid to sulfinimines (isosteric with sulfoxides but far more unstable) or phosphorus compounds (such as triphenylphosphine) can be aminated to phosphine imides via the intermediate aminotriphenylphosphonium hydrogen sulfate. [17]

Phosphinimine.svg

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 primaren Sulfonamiden aus Sulfinaten Sulfonamide aus Sulfinaten.svg
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 von HOSA mit Carbonylverbindungen.svg
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 aus Cycloheptanon.svg
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.svg
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 Diaziridine.svg
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 1,2-Benzisoxazol.svg
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.svg
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]

Related Research Articles

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In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Oxime</span> Organic compounds of the form >C=N–OH

In organic chemistry, an oxime is an organic compound belonging to the imines, with the general formula RR’C=N−OH, where R is an organic side-chain and R' may be hydrogen, forming an aldoxime, or another organic group, forming a ketoxime. O-substituted oximes form a closely related family of compounds. Amidoximes are oximes of amides with general structure R1C(=NOH)NR2R3.

<span class="mw-page-title-main">Hydroxylamine</span> Inorganic compound

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Hydrazones are a class of organic compounds with the structure R1R2C=N−NH2. They are related to ketones and aldehydes by the replacement of the oxygen =O with the =N−NH2 functional group. They are formed usually by the action of hydrazine on ketones or aldehydes.

<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

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In organic chemistry, a nitrile is any organic compound that has a −C≡N functional group. The name of the compound is composed of a base, which includes the carbon of the −C≡N, suffixed with "nitrile", so for example CH3CH2C≡N is called "propionitrile". The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

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<span class="mw-page-title-main">Iminium</span> Polyatomic ion of the form >C=N< and charge +1

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References

  1. ↑ Perrin, D. D., ed. (1982) [1969]. Ionisation Constants of Inorganic Acids and Bases in Aqueous Solution. IUPAC Chemical Data (2nd ed.). Oxford: Pergamon (published 1984). Entry 115. ISBN   0-08-029214-3. LCCN   82-16524.
  2. 1 2 Matsuguma, Harold J.; Audrieth, Ludwig F.; Wehrmeister, Herbert L. (1957). "Hydroxylamine‐ O ‐Sulfonic Acid". Inorganic Syntheses. Vol. 5. pp. 122–125. doi:10.1002/9780470132364.ch32. ISBN   9780470132364.{{cite book}}: |journal= ignored (help)
  3. 1 2 3 Wiberg, Egon; Wiberg, Nils (2001). "Sulfur Compounds of Nitrogen". Inorganic Chemistry. Academic Press. pp. 675–677. ISBN   978-0-12-352651-9.
  4. 1 2 Wallace, Raymond G. (1980). "Hydroxylamine-O-sulfonic acid – a versatile synthetic reagent". Aldrichimica Acta . 13 (1): 3–11.
  5. ↑ Rademacher, P. (2014). "Product Class 7: Hydrazines and Hydrazinium Salts (40.7.1.1.9.2 – Using Hydroxylamine-O-sulfonic Acids". In Enders, Dieter; Schaumann, E. (eds.). Compounds with One Saturated Carbon–Heteroatom Bond: Amine N-Oxides, Haloamines, Hydroxylamines and Sulfur Analogues, and Hydrazines. Science of Synthesis: Houben-Weyl Methods of Molecular Transformations. Vol. 40b. Georg Thieme Verlag. p. 1171. ISBN   978-3-13-172181-5.
  6. ↑ USpatent 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. ↑ Sommer, F.; Schulz, O. F.; Nassau, M. (1925). "Über die Sulfoperamidsäure" [About Sulfoperamic Acid]. Z. Anorg. Allg. Chem. (in German). 147 (1): 142–155. doi:10.1002/zaac.19251470115.
  8. ↑ Rathke, Michael W.; Millard, Alan A. (1978). "Boranes in functionalization of olefins to amines: 3-Pinanamine (Bicyclo[3.1.1]heptan-3-amine, 2,6,6-trimethyl-)". Organic Syntheses . 58: 32. doi:10.15227/orgsyn.058.0032 ; Collected Volumes, vol. 6, p. 943.
  9. ↑ Erdik, Ender; Saczewski, Jarosław; Libman, Anna; Kürti László (27 July 2023). "Hydroxylamine-O-Sulfonic Acid". Reagents for Organic Synthesis (Online 3rd ed.). Wiley. doi:10.1002/047084289X.rh058.pub3.
  10. ↑ Baenziger, Norman C.; Belt, Roger F.; Goebel, Carol V. (1967). "Crystal structure of hydroxylamine-O-sulfonic acid". Inorg. Chem. 6 (3): 511–514. doi:10.1021/ic50049a017.
  11. ↑ Erdik, Ender (2001). "Hydroxylamine-O-sulfonic Acid". Hydroxylamine-O-Sulfonic Acid. Encyclopedia of Reagents for Organic Synthesis . doi:10.1002/047084289X.rh058. ISBN   978-0-471-93623-7.
  12. ↑ R. Gösl; A. Meuwsen (1963). "1-Aminopyridinium iodide". Org. Synth. (in German). 43: 1. doi:10.15227/orgsyn.043.0001.
  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. ↑ J. Streith (1977). "The photochemistry of aromatic-N-ylides. Rearrangement and fragmentation patterns". Pure Appl. Chem. (in German). 49 (3): 305–315. doi: 10.1351/pac197749030305 .
  15. ↑ Campbell, C.D.; Rees, C.W. (1969). "Reactive intermediates. Part I. Synthesis and oxidation of 1- and 2-aminobenzotriazole". J. Chem. Soc. C . 1969 (5): 742–747. doi:10.1039/J39690000742.
  16. ↑ T.M. Klapötke; D.G. Piercey; J. Stierstorfer (2012). "Amination of energetic anions: high-performing energetic materials". Dalton Trans. (in German). 41 (31): 9451–9459. doi:10.1039/C2DT30684K. PMID   22751656.
  17. ↑ R. Appel; W. Büchner; E. Guth (1958). "Zur Kenntnis des Imins, I. Über Phosphinimine und Sulfinimine". Justus Liebigs Ann. Chem. (in German). 618 (1): 53–58. doi:10.1002/jlac.19586180107.
  18. ↑ S.L. Graham; T.H. Scholz (1986). "The reaction of sulfinic acid salts with hydroxylamine-O-sulfonic acid. A useful synthesis of primary sulfonamides". Synthesis (in German). 1986 (2): 1031–1032. doi:10.1055/s-1986-31862.
  19. ↑ J. Streith; C. Fizet (1977). "Nucleophilic versus electrophilic properties of the nitrogen atom in O-sulfonyl-hydroxylamine derivatives". Tetrahedron Lett. (in German). 18 (37): 3297–3300. doi:10.1016/S0040-4039(01)83223-8.
  20. ↑ C. Fizet; J. Streith (1974). "Hydroxylamine-O-sulfonic acid: A convenient reagent for the oxidative conversion of aldehydes into nitriles". Tetrahedron Lett. (in German). 15 (36): 3187–3188. doi:10.1016/S0040-4039(01)91857-X.
  21. ↑ G.A. Olah; A.P. Fung (1985). "Hexahydro-2-(1H)-azocinone". Org. Synth. (in German). 63: 188. doi:10.15227/orgsyn.063.0188.
  22. ↑ E. Schmitz; R. Ohme (1965). "3,3-Pentamethylenediaziridine". Org. Synth. (in German). 45: 83. doi:10.15227/orgsyn.045.0083.
  23. ↑ A.W. Beebe; E.F. Dohmeier; G. Moura-Letts (2015). "Diastereoselective synthesis of substituted diaziridines from simple ketones and aldehydes". Chem. Commun. (in German). 51 (70): 13511–13514. doi:10.1039/C5CC04813C. PMID   26216745.
  24. ↑ D.S. Kemp; R.B. Woodward (1965). "The N-ethylbenzisoxazolium cation—I : Preparation and reactions with nucleophilic species". Tetrahedron (in German). 21 (11): 3019–3035. doi:10.1016/S0040-4020(01)96921-2.
  25. ↑ L.E. Evans; M.D. Cheeseman; K. Jones (2012). "N–N Bond-Forming Cyclization for the One-Pot Synthesis of N-Aryl[3,4-d]pyrazolopyrimidines". Org. Lett. (in German). 14 (13): 3546–3549. doi:10.1021/ol301561a. PMC   3390909 . PMID   22734502.
  26. ↑ C. Morrill; S. Babu; N.G. Almstead; Y.-C. Moon (2013). "Synthesis of 1,4-disubstituted pyrazolo[3,4-d]pyrimidines from 4,6-dichloropyrimidine-5-carboxaldehyde: insights into selectivity and reactivity". Synthesis (in German). 45 (13): 1791–1806. doi:10.1055/s-0033-1338862.
  27. ↑ M. Saqib; W. Gao; J. Lai; L. Qi; S. Majeed; M.R.H.S. Gilani; G. Xu (2015). "Hydroxylamine-O-sulfonic acid as an efficient coreactant for luminol chemiluminescence for selective and sensitive detection". Chem. Commun. (in German). 51 (30): 6536–6539. doi:10.1039/C5CC01090J. PMID   25766485.
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