羟胺-O-磺酸

羥胺-O-磺酸
英文名	Hydroxylamine-O-sulfonic acid
識別
CAS編號	2950-43-8
PubChem	76284
ChemSpider	68763
SMILES	NOS(=O)(=O)O;
EINECS	220-971-6
性質
化學式	H3NO4S
摩爾質量	113.09 g·mol−1
外觀	白色至米色固體
密度	2.2 g/cm3
熔點	210 °C（分解）
溶解性（水）	675 g/L，緩慢分解
溶解性	可溶於甲醇和DMSO; 不溶於非極性溶劑
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

羥胺-O-磺酸是化學式 H₃NO₄S的無機化合物，可以由羥胺和發煙硫酸反應而成。^[4]它是白色、可溶於水、易潮解的固體，以兩性離子⁺H₃NOSO₃⁻存在。^[5]它被用作胺化試劑，也用於把醛轉化成腈，把環酮轉化成內酰胺，以及各種含氮雜環的合成。^[5]^[6]^[7]

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製備

實驗室的羥胺-O-磺酸是由羥胺和發煙硫酸的反應製備的，^[4]而工業生產羥胺-O-磺酸的生產過程也是這樣。^[8]

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

羥胺和氯磺酸反應也可以得到羥胺-O-磺酸^[5]。

結構

類似氨基磺酸（H₃N⁺SO₃⁻）和氨基酸，羥胺-O-磺酸在固態下以兩性離子 H₃N⁺OSO₃⁻的形式存在。^[9]

反應

羥胺-O-磺酸在鹼性環境下是親核體，在酸性條件下是親電體。^[6]^[10]

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

胺化反應

羥胺-O-磺酸和一級胺、二級胺反應會分別產生對應的肼。舉個例子，它和哌啶反應，生成N-氨基哌啶，產率96%。^[11]

Synthesis of N-Aminopiperidin with HOSA

它和吡啶的反應則會生成1-氨基吡啶鎓鹽。^[12]

Thumb — Synthesis of 1-Aminopyridin with HOSA

苯並三唑被羥胺-O-磺酸N-胺化，產生1-氨基苯並三唑（主產物）和2-氨基苯並三唑。1-氨基苯並三唑被乙酸鉛(IV)氧化會產生苯炔，然後迅速二聚成聯苯烯。^[13]

像是四唑的缺電子雜環化合物可以被羥胺-O-磺酸N-胺化，而更缺電子的5-硝基四唑則只能和更強的胺化試劑（如O-對甲苯磺酰基羥胺）反應。^[14]

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

硫醚可以被羥胺-O-磺酸胺化成亞氨基硫醚（結構和亞碸相似但很不穩定），而膦則會被胺化成亞氨基膦（英語：phosphine imide）。^[15]

Synthesis of Sulfiminen with HOSA

羥胺-O-磺酸和亞磺酸鹽在乙酸鈉溶液中反應可以得到磺酰胺，產率很高。^[16]

Synthesis of primären Sulfonamiden aus Sulfinaten

和羰基化合物的反應

在室溫下，羥胺-O-磺酸和酮、醛的反應會產生對應的肟-O-磺酸或其鹽。^[17]在更高溫下，醛肟-O-磺酸會和硫酸發生消去反應，生成腈。^[18]

脂肪酮在同樣的條件下會產生酮肟，芳香酮則會通過貝克曼重排反應重排成酰胺。環酮和羥胺-O-磺酸在酸性條件（例如濃甲酸中）回流加熱幾個小時，可以得到內酰胺。^[19]

在鹼性條件和一級胺存在下，羥胺-O-磺酸可以和醛、酮（例如環己酮）^[20]反應生成二氮雜環丙烷，而二氮雜環丙烷很容易被氧化成更穩定的二氮雜環丙烯。

3,3-Pentamethylendiaziridin durch Reaktion of Cyclohexanon mit HOSA

這個反應可用於生產取代的二氮雜環丙烷，並有對映選擇性。^[21]

苯並異噁唑（英語：1,2-Benzisoxazole）可以由羥胺-O-磺酸和水楊醛反應而成，^[22]而苯並異噁唑是抗精神病藥利培酮和帕利哌酮以及抗癲癇藥（英語：anticonvulsant）唑尼沙胺的母體化合物。

其它反應

魯米諾/氯化亞鈷體系發出的光可以被羥胺-O-磺酸顯著增強。^[23]

參考資料

[1]
來源：Sigma-Aldrich Co., product no. 480975 .
[2]
Datenblatt Hydroxylamin-O-sulfonsäure zur Synthese [Hydroxylamin-O-sulfonsäure zur Synthese安全信息單（MSDS）] (PDF). Herstellers Merck （德語）.
[3]
Erdik, Ender; Saczewski, Jarosław, Hydroxylamine-O-sulfonic Acid, Chichester, UK: John Wiley & Sons, Ltd, 2013-04-22, doi:10.1002/047084289x.rh058.pub2
[4]
Matsuguma, Harold J.; Audrieth, Ludwig F.; Wehrmeister, Herbert L. Hydroxylamine-O-Sulfonic Acid. Inorganic Syntheses 5. 1957: 122–125. ISBN 9780470132364. doi:10.1002/9780470132364.ch32.
[5]
Wiberg, Egon; Wiberg, Nils. Sulfur Compounds of Nitrogen. Inorganic Chemistry. Academic Press. 2001: 675–677. ISBN 978-0-12-352651-9.
[6]
Wallace, Raymond G. Hydroxylamine-O-sulfonic acid – a versatile synthetic reagent. Aldrichimica Acta. 1980, 13 (1): 3–11 [2022-09-08]. （原始內容存檔於2019-04-04）.
[7]
Rademacher, P. Product Class 7: Hydrazines and Hydrazinium Salts (40.7.1.1.9.2 – Using Hydroxylamine-O-sulfonic Acids. Enders, Dieter; Schaumann, E. (編). 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 40b. Georg Thieme Verlag. 2014: 1171. ISBN 978-3-13-172181-5.
[8]
US patent 3281209,Wehrmeister, Herbert L. & Harold I. Yalowitz,「Process for the preparation of hydroxylamine-O-sulfonic acid」,發表於1966-10-25,發行於1966-10-25,指定於Commercial Solvents Corporation （頁面存檔備份，存於互聯網檔案館）
[9]
Baenziger, Norman C.; Belt, Roger F.; Goebel, Carol V. Crystal structure of hydroxylamine-O-sulfonic acid. Inorg. Chem. 1967, 6 (3): 511–514. doi:10.1021/ic50049a017.
[10]
Erdik, Ender. Hydroxylamine-O-Sulfonic Acid. Encyclopedia of Reagents for Organic Synthesis. 2001. ISBN 978-0-471-93623-7. doi:10.1002/047084289X.rh058.
[11]
Labarthe, E.; Bougrine, A. J.; Pasquet, Véronique; Delalu, H. A New Strategy for the Preparation of N-Aminopiperidine Using Hydroxylamine-O-Sulfonic Acid: Synthesis, Kinetic Modelling, Phase Equilibria, Extraction and Processes. Advances in Chemical Engineering and Science (Scientific Research Publishing, Inc.). 2013, 03 (02): 157–163. ISSN 2160-0392. doi:10.4236/aces.2013.32019.
[12]
R. Gösl; A. Meuwsen. 1-Aminopyridinium iodide. Org. Synth. 1963, 43: 1. doi:10.15227/orgsyn.043.0001 （德語）.
[13]
Campbell, C.D.; Rees, C.W. Reactive intermediates. Part I. Synthesis and oxidation of 1- and 2-aminobenzotriazole. J. Chem. Soc. C. 1969, 1969 (5): 742–747. doi:10.1039/J39690000742.
[14]
T.M. Klapötke; D.G. Piercey; J. Stierstorfer. Amination of energetic anions: high-performing energetic materials. Dalton Trans. 2012, 41 (31): 9451–9459. PMID 22751656. doi:10.1039/C2DT30684K （德語）.
[15]
R. Appel; W. Büchner; E. Guth. Zur Kenntnis des Imins, I. Über Phosphinimine und Sulfinimine. Justus Liebigs Ann. Chem. 1958, 618 (1): 53–58. doi:10.1002/jlac.19586180107 （德語）.
[16]
S.L. Graham; T.H. Scholz. The reaction of sulfinic acid salts with hydroxylamine-O-sulfonic acid. A useful synthesis of primary sulfonamides. Synthesis. 1986, 1986 (2): 1031–1032. doi:10.1055/s-1986-31862 （德語）.
[17]
J. Streith; C. Fizet. Nucleophilic versus electrophilic properties of the nitrogen atom in O-sulfonyl-hydroxylamine derivatives. Tetrahedron Lett. 1977, 18 (37): 3297–3300. doi:10.1016/S0040-4039(01)83223-8 （德語）.
[18]
C. Fizet; J. Streith. Hydroxylamine-O-sulfonic acid: A convenient reagent for the oxidative conversion of aldehydes into nitriles. Tetrahedron Lett. 1974, 15 (36): 3187–3188. doi:10.1016/S0040-4039(01)91857-X （德語）.
[19]
G.A. Olah; A.P. Fung. Hexahydro-2-(1H)-azocinone. Org. Synth. 1985, 63: 188. doi:10.15227/orgsyn.063.0188 （德語）.
[20]
E. Schmitz; R. Ohme. 3,3-Pentamethylenediaziridine. Org. Synth. 1965, 45: 83. doi:10.15227/orgsyn.045.0083 （德語）.
[21]
A.W. Beebe; E.F. Dohmeier; G. Moura-Letts. Diastereoselective synthesis of substituted diaziridines from simple ketones and aldehydes. Chem. Commun. 2015, 51 (70): 13511–13514. PMID 26216745. doi:10.1039/C5CC04813C （德語）.
[22]
D.S. Kemp; R.B. Woodward. The N-ethylbenzisoxazolium cation—I : Preparation and reactions with nucleophilic species. Tetrahedron. 1965, 21 (11): 3019–3035. doi:10.1016/S0040-4020(01)96921-2 （德語）.
[23]
M. Saqib; W. Gao; J. Lai; L. Qi; S. Majeed; M.R.H.S. Gilani; G. Xu. Hydroxylamine-O-sulfonic acid as an efficient coreactant for luminol chemiluminescence for selective and sensitive detection. Chem. Commun. 2015, 51 (30): 6536–6539. PMID 25766485. doi:10.1039/C5CC01090J （德語）.

[Sigma-1] [1]
來源：Sigma-Aldrich Co., product no. 480975 .

[Merck-2] [2]
Datenblatt Hydroxylamin-O-sulfonsäure zur Synthese [Hydroxylamin-O-sulfonsäure zur Synthese安全信息單（MSDS）] (PDF). Herstellers Merck （德語）.

[Erdik-3] [3]
Erdik, Ender; Saczewski, Jarosław, Hydroxylamine-O-sulfonic Acid, Chichester, UK: John Wiley & Sons, Ltd, 2013-04-22, doi:10.1002/047084289x.rh058.pub2

[LabPrep-4] [4]
Matsuguma, Harold J.; Audrieth, Ludwig F.; Wehrmeister, Herbert L. Hydroxylamine-O-Sulfonic Acid. Inorganic Syntheses 5. 1957: 122–125. ISBN 9780470132364. doi:10.1002/9780470132364.ch32.

[Wiberg-5] [5]
Wiberg, Egon; Wiberg, Nils. Sulfur Compounds of Nitrogen. Inorganic Chemistry. Academic Press. 2001: 675–677. ISBN 978-0-12-352651-9.

[Wallace-6] [6]
Wallace, Raymond G. Hydroxylamine-O-sulfonic acid – a versatile synthetic reagent. Aldrichimica Acta. 1980, 13 (1): 3–11 [2022-09-08]. （原始內容存檔於2019-04-04）.

[7] [7]
Rademacher, P. Product Class 7: Hydrazines and Hydrazinium Salts (40.7.1.1.9.2 – Using Hydroxylamine-O-sulfonic Acids. Enders, Dieter; Schaumann, E. (編). 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 40b. Georg Thieme Verlag. 2014: 1171. ISBN 978-3-13-172181-5.

[8] [8]
US patent 3281209,Wehrmeister, Herbert L. & Harold I. Yalowitz,「Process for the preparation of hydroxylamine-O-sulfonic acid」,發表於1966-10-25,發行於1966-10-25,指定於Commercial Solvents Corporation （頁面存檔備份，存於互聯網檔案館）

[9] [9]
Baenziger, Norman C.; Belt, Roger F.; Goebel, Carol V. Crystal structure of hydroxylamine-O-sulfonic acid. Inorg. Chem. 1967, 6 (3): 511–514. doi:10.1021/ic50049a017.

[10] [10]
Erdik, Ender. Hydroxylamine-O-Sulfonic Acid. Encyclopedia of Reagents for Organic Synthesis. 2001. ISBN 978-0-471-93623-7. doi:10.1002/047084289X.rh058.

[11] [11]
Labarthe, E.; Bougrine, A. J.; Pasquet, Véronique; Delalu, H. A New Strategy for the Preparation of N-Aminopiperidine Using Hydroxylamine-O-Sulfonic Acid: Synthesis, Kinetic Modelling, Phase Equilibria, Extraction and Processes. Advances in Chemical Engineering and Science (Scientific Research Publishing, Inc.). 2013, 03 (02): 157–163. ISSN 2160-0392. doi:10.4236/aces.2013.32019.

[12] [12]
R. Gösl; A. Meuwsen. 1-Aminopyridinium iodide. Org. Synth. 1963, 43: 1. doi:10.15227/orgsyn.043.0001 （德語）.

[13] [13]
Campbell, C.D.; Rees, C.W. Reactive intermediates. Part I. Synthesis and oxidation of 1- and 2-aminobenzotriazole. J. Chem. Soc. C. 1969, 1969 (5): 742–747. doi:10.1039/J39690000742.

[14] [14]
T.M. Klapötke; D.G. Piercey; J. Stierstorfer. Amination of energetic anions: high-performing energetic materials. Dalton Trans. 2012, 41 (31): 9451–9459. PMID 22751656. doi:10.1039/C2DT30684K （德語）.

[15] [15]
R. Appel; W. Büchner; E. Guth. Zur Kenntnis des Imins, I. Über Phosphinimine und Sulfinimine. Justus Liebigs Ann. Chem. 1958, 618 (1): 53–58. doi:10.1002/jlac.19586180107 （德語）.

[16] [16]
S.L. Graham; T.H. Scholz. The reaction of sulfinic acid salts with hydroxylamine-O-sulfonic acid. A useful synthesis of primary sulfonamides. Synthesis. 1986, 1986 (2): 1031–1032. doi:10.1055/s-1986-31862 （德語）.

[17] [17]
J. Streith; C. Fizet. Nucleophilic versus electrophilic properties of the nitrogen atom in O-sulfonyl-hydroxylamine derivatives. Tetrahedron Lett. 1977, 18 (37): 3297–3300. doi:10.1016/S0040-4039(01)83223-8 （德語）.

[18] [18]
C. Fizet; J. Streith. Hydroxylamine-O-sulfonic acid: A convenient reagent for the oxidative conversion of aldehydes into nitriles. Tetrahedron Lett. 1974, 15 (36): 3187–3188. doi:10.1016/S0040-4039(01)91857-X （德語）.

[19] [19]
G.A. Olah; A.P. Fung. Hexahydro-2-(1H)-azocinone. Org. Synth. 1985, 63: 188. doi:10.15227/orgsyn.063.0188 （德語）.

[20] [20]
E. Schmitz; R. Ohme. 3,3-Pentamethylenediaziridine. Org. Synth. 1965, 45: 83. doi:10.15227/orgsyn.045.0083 （德語）.

[21] [21]
A.W. Beebe; E.F. Dohmeier; G. Moura-Letts. Diastereoselective synthesis of substituted diaziridines from simple ketones and aldehydes. Chem. Commun. 2015, 51 (70): 13511–13514. PMID 26216745. doi:10.1039/C5CC04813C （德語）.

[22] [22]
D.S. Kemp; R.B. Woodward. The N-ethylbenzisoxazolium cation—I : Preparation and reactions with nucleophilic species. Tetrahedron. 1965, 21 (11): 3019–3035. doi:10.1016/S0040-4020(01)96921-2 （德語）.

[23] [23]
M. Saqib; W. Gao; J. Lai; L. Qi; S. Majeed; M.R.H.S. Gilani; G. Xu. Hydroxylamine-O-sulfonic acid as an efficient coreactant for luminol chemiluminescence for selective and sensitive detection. Chem. Commun. 2015, 51 (30): 6536–6539. PMID 25766485. doi:10.1039/C5CC01090J （德語）.

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