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]
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]
Reaktivität of Hydroxylamine-O-sulfonsäure als Elektrophil und als Nukleophil
Aminations
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
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
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
Electron deficientheterocycles, 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
In the N-amination of the unsubstituted tetrazole, a mixture of 1-amino- and 2-aminotetrazole is obtained.
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
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
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
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
The reaction also provides substituted aziridines from simple aldehydes and ketones with high yield and diastereoselectivity.[23]
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
^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. ISBN0-08-029214-3. LCCN82-16524.
^ abMatsuguma, 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. ISBN9780470132364. {{cite book}}: |journal= ignored (help)
^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
^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 (inactive 1 November 2024).{{cite encyclopedia}}: CS1 maint: DOI inactive as of November 2024 (link)
^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.
^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.
^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.
^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.
^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.
^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.
^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. PMID25766485.
