羟胺-O-磺酸

羟胺-O-磺酸
英文名 Hydroxylamine-O-sulfonic acid
识别
CAS号 2950-43-8
PubChem 76284
ChemSpider 68763
SMILES
 
  • NOS(=O)(=O)O
EINECS 220-971-6
性质
化学式 H3NO4S
摩尔质量 113.09 g·mol−1
外观 白色至米色固体[1]
密度 2.2 g/cm3[2]
熔点 210 °C(分解)[1]
溶解性 675 g/L,缓慢分解[2]
溶解性 可溶于甲醇DMSO[3]
不溶于非极性溶剂[3]
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

羟胺-O-磺酸化学式 H3NO4S的无机化合物,可以由羟胺发烟硫酸反应而成。[4]它是白色、可溶于水、易潮解的固体,以两性离子+H3NOSO3存在。[5]它被用作胺化试剂,也用于把转化成,把环转化成内酰胺,以及各种含氮杂环的合成。[5][6][7]

制备

实验室的羟胺-O-磺酸是由羟胺发烟硫酸的反应制备的,[4]而工业生产羟胺-O-磺酸的生产过程也是这样。[8]

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

羟胺和氯磺酸反应也可以得到羟胺-O-磺酸[5]

结构

类似氨基磺酸(H3N+SO3)和氨基酸,羟胺-O-磺酸在固态下以两性离子 H3N+OSO3的形式存在。[9]

反应

羟胺-O-磺酸在碱性环境下是亲核体,在酸性条件下是亲电体[6][10]

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

胺化反应

羟胺-O-磺酸和伯胺、仲胺反应会分别产生对应的。举个例子,它和哌啶反应,生成N-氨基哌啶,产率96%。[11]

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

它和吡啶的反应则会生成1-氨基吡啶𬭩盐。[12]

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

苯并三唑被羟胺-O-磺酸N-胺化,产生1-氨基苯并三唑(主产物)和2-氨基苯并三唑。1-氨基苯并三唑被乙酸铅(IV)氧化会产生苯炔,然后迅速二聚联苯烯[13]

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

像是四唑缺电子杂环化合物可以被羟胺-O-磺酸N-胺化,而更缺电子的5-硝基四唑则只能和更强的胺化试剂(如O-对甲苯磺酰基羟胺)反应。[14]

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

硫醚可以被羟胺-O-磺酸胺化成亚氨基硫醚(结构和亚砜相似但很不稳定),而则会被胺化成亚氨基膦英语phosphine imide[15]

Synthesis of Sulfiminen with HOSA
Synthesis of Sulfiminen with HOSA

羟胺-O-磺酸和亚磺酸盐在乙酸钠溶液中反应可以得到磺酰胺,产率很高。[16]

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

和羰基化合物的反应

在室温下,羟胺-O-磺酸和酮、醛的反应会产生对应的肟-O-磺酸或其盐。[17]在更高温下,醛肟-O-磺酸会和硫酸发生消除反应,生成[18]

Reaktion of HOSA with Carbonylverbindungen
Reaktion of HOSA with Carbonylverbindungen

脂肪酮在同样的条件下会产生酮肟,芳香酮则会通过贝克曼重排反应重排成酰胺。环酮和羟胺-O-磺酸在酸性条件(例如浓甲酸中)回流加热几个小时,可以得到内酰胺[19]

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

在碱性条件和伯胺存在下,羟胺-O-磺酸可以和醛、酮(例如环己酮[20]反应生成二氮杂环丙烷,而二氮杂环丙烷很容易被氧化成更稳定的二氮杂环丙烯

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

这个反应可用于生产取代的二氮杂环丙烷,并有对映选择性。[21]

Synthesis of Diaziridinen with HOSA
Synthesis of Diaziridinen with HOSA

1,2-苯并异𫫇唑可以由羟胺-O-磺酸和水杨醛反应而成,[22]而苯并异𫫇唑是抗精神病药利培酮帕利哌酮以及抗癫痫药英语anticonvulsant唑尼沙胺的母体化合物。

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

其它反应

鲁米诺/氯化亚钴体系发出的光可以被羟胺-O-磺酸显著增强。[23]

参考资料

  1. ^ 1.0 1.1 来源:Sigma-Aldrich Co., product no. 480975 .
  2. ^ 2.0 2.1 Datenblatt Hydroxylamin-O-sulfonsäure zur Synthese [Hydroxylamin-O-sulfonsäure zur Synthese安全信息单(MSDS)] (PDF). Herstellers Merck (德语). 
  3. ^ 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. ^ 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. ^ 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. ^ 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]. (原始内容存档于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. (编). 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」,发表于1966-10-25,发行于1966-10-25,指定于Commercial Solvents Corporation 页面存档备份,存于互联网档案馆
  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 (德语). 
  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 (德语). 
  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 (德语). 
  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 (德语). 
  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 (德语). 
  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 (德语). 
  19. ^ G.A. Olah; A.P. Fung. Hexahydro-2-(1H)-azocinone. Org. Synth. 1985, 63: 188. doi:10.15227/orgsyn.063.0188 (德语). 
  20. ^ E. Schmitz; R. Ohme. 3,3-Pentamethylenediaziridine. Org. Synth. 1965, 45: 83. doi:10.15227/orgsyn.045.0083 (德语). 
  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 (德语). 
  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 (德语). 
  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 (德语). 

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