弗氏盐

弗氏盐是一种无机化合物，化学式 (K4[ON(SO3)2]2)，有时写作 (K2[NO(SO3)2])。它是一种亮黄棕色固体，但水溶液是亮紫色的。 相关的钠盐亚硝基二磺酸钠（简称NDS，化学式 Na2ON(SO3)2，CAS号 29554-37-8）也被称为弗氏盐。 弗氏盐作为一种长寿命的自由基，是电子自旋共振 (EPR) 的标准。其强烈的EPR谱线由三条等强度的线主导，间距约为 13 G（1.3 mT）。 弗氏盐可用于某些氧化反应，例如某些苯胺或苯酚的氧化。它也允许肽和基于肽的水凝胶（英语：Hydrogel）的聚合和交联。 它还可以用作研究中过氧自由基的模型，以研究各种天然产品中抗氧化作用的机制。 弗氏盐可以由羟胺二磺酸开始制备而成。氧化它的共轭碱可以得到紫色的双阴离子： HON(SO3H)2 → [HON(SO3)2]2− + 2 H+ 2 [HON(SO3)2]2− + PbO2 → 2 [ON(SO3)2]2− + PbO + H2O 羟胺二磺酸盐则是由亚硝酸盐和亚硫酸氢盐反应而成的。氧化反应通常是在低温下进行的，可以通过化学方法或电解达成。 其它制备方法： HNO2 + 2 HSO− 3 → HON(SO 3)2− 2 + H2O 3 HON(SO 3)2− 2 + MnO− 4 + H+ → 3 ON(SO 3)2− 2 + MnO2 + 2 H2O 2 ON(SO 3)2− 2 + 4 K+ → K4[ON(SO3)2]2 弗氏盐是在1845年由埃德蒙·弗雷米 (1814–1894)发现的。 Greenwood, Norman Neill; Earnshaw, Alan. Chemistry of the elements. 2016. ISBN 978-0-7506-3365-9. OCLC 1040112384 （英语）.  Synthesis and Characterization of Potassium Nitrosodisulfonate, Frémy's Salt (PDF). tripod.com. [2021-12-03]. （原始内容 (PDF)存档于2010-09-23）.  Wehrli PA, Pigott F. Oxidation with the nitrosodisulfonate radical. I. Preparation and use of sodium nitrosodisulfonate: trimethyl-p-benzoquinone. Organic Syntheses. 1972, 52: 83. doi:10.15227/orgsyn.052.0083.  Wertz JE, Bolton JR. Electron Spin Resonance: Elementary Theory and Practical Applications. New York: McGraw-Hill. 1972. ISBN 978-0-07-069454-5.  See page 463 for information on intensity measurements and page 86 for an EPR spectrum of Frémy's salt. Colacicchi S, Carnicelli V, Gualtieri G, Di Giulio A. EPR study of Frémy's salt nitroxide reduction by ascorbic acid; influence of bulk pH values. Res. Chem. Intermed. 2000, 26 (9): 885–896. S2CID 98775951. doi:10.1163/156856700X00372.  Zielonka J, Zhao H, Xu Y, Kalyanaraman B. Mechanistic similarities between oxidation of hydroethidine by Frémy's salt and superoxide: stopped-flow optical and EPR studies. Free Radical Biology & Medicine. October 2005, 39 (7): 853–863. PMID 16140206. doi:10.1016/j.freeradbiomed.2005.05.001.  Zimmer H, Lankin DC, Horgan SW. Oxidations with potassium nitrosodisulfonate (Frémy's radical). Teuber reaction.. Chemical Reviews. 1971, 71 (2): 229–246. doi:10.1021/cr60270a005.  Islam I, Skibo EB, Dorr RT, Alberts DS. Structure-activity studies of antitumor agents based on pyrrolo[1,2-a]benzimidazoles: new reductive alkylating DNA cleaving agents. Journal of Medicinal Chemistry. October 1991, 34 (10): 2954–2961. PMID 1920349. doi:10.1021/jm00114a003.  Teuber HJ, Benz S. Reaktionen mit Nitrosodisulfonat, XXXVI. Chinolin-chinone-(5.6) aus 5-Hydroxy-chinolinen. Chem. Ber. 1967, 100 (9): 2918–2929. doi:10.1002/cber.19671000916 （德语）. [失效連結] Teuber HJ. Use of dipotassium nitrosodisulfonate (Frémy's salt): 4,5-dimethyl-o-benzoquinone. Org. Synth. 1972, 52: 88. doi:10.15227/orgsyn.052.0088.  Xue W, Warshawsky D, Rance M, Jayasimhulu K. A metabolic activation mechanism of 7H-dibenzo[c,g]carbozole via o-quinone. Part 1: synthesis of 7H-dibenzo[c,g]carbozole-3,4-dione and reactions with nucleophiles. Polycyclic Aromatic Compounds. 2002, 22 (3–4): 295–300. S2CID 95507636. doi:10.1080/10406630290026957.  Wilchek M, Miron T. Mussel-inspired new approach for polymerization and cross-linking of peptides and proteins containing tyrosines by Frémy's salt oxidation. Bioconjugate Chemistry. March 2015, 26 (3): 502–510. PMID 25692389. doi:10.1021/bc5006152.  Fichman G, Schneider JP. Utilizing Frémy's Salt to Increase the Mechanical Rigidity of Supramolecular Peptide-Based Gel Networks. Frontiers in Bioengineering and Biotechnology. 2021, 8: 594258. PMC 7813677 . PMID 33469530. doi:10.3389/fbioe.2020.594258  （英语）.  Liu ZL, Han ZX, Chen P, Liu YC. Stopped-flow ESR study on the reactivity of vitamin E, vitamin C and its lipophilic derivatives towards Frémy's salt in micellar systems. Chemistry and Physics of Lipids. November 1990, 56 (1): 73–80. PMID 1965427. doi:10.1016/0009-3084(90)90090-E.  参见： Frémy, E. (1845) "Sur un nouvelle série d'acides formés d'oxygène, de soufre, d'hydrogène et de d'azote" （页面存档备份，存于互联网档案馆） (On a new series of acids formed from oxygen, sulfur, hydrogen, and nitrogen), Annales de Chimie et de Physique, 3rd series, 15 : 408-488. Frémy's salt appears on p. 447 （页面存档备份，存于互联网档案馆）, where it's called "sulfazidate de potasse". Frémy, E. (1845) "Sur un nouvelle série d'acides formés d'oxygène, de soufre, d'hydrogène et de d'azote" （页面存档备份，存于互联网档案馆） (On a new series of acids formed from oxygen, sulfur, hydrogen, and nitrogen), Comptes rendus, 21 : 218–226. This is a condensed version of the article that appeared in Annales de Chimie et de Physique. "Séances académiques," L'Institut, no. 604, 23 July 1845, pp. 265–266. （页面存档备份，存于互联网档案馆） "Séances académiques," L'Institut, no. 619, 12 November 1845, pp. 393. （页面存档备份，存于互联网档案馆） Here a committee of the French Academy of Sciences reviewed Frémy's findings. Edward Divers and Tamemasa Haga (1900) "Identification and constitution of Frémy's sulphazotised salts of potassium," （页面存档备份，存于互联网档案馆） Journal of the Chemical Society, Transactions, 77 : 440-446. doi:10.1039/CT9007700440 Here, correct formulae for Frémy's salts are presented. On p. 445 （页面存档备份，存于互联网档案馆）, the salt that Frémy called sulfazidate is identified as ON(SO3K)2. Morey J. Undergraduate Experiments with a Long-Lived Radical (Frémy's salt): Synthesis of 1,4-Benzoquinones by Degradative Oxidation of p-Hydroxybenzyl Alcohols. J. Chem. Educ. 1988, 65 (7): 627–629. Bibcode:1988JChEd..65..627M. doi:10.1021/ed065p627.