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Frémy's salt

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Frémy's salt
Names
IUPAC name Potassium nitrosodisulfonate
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.034.729 Edit this at Wikidata
EC Number
  • 238-219-0
PubChem CID
UNII
InChI
  • InChI=1S/2K.H2NO7S2/c;;2-1(9(3,4)5)10(6,7)8/h;;(H,3,4,5)(H,6,7,8)/q2*+1;/p-2Key: IHSLHAZEJBXKMN-UHFFFAOYSA-L
SMILES
  • N()(S(=O)(=O))S(=O)(=O)..
Properties
Chemical formula K2NO(SO3)2
Molar mass 268.33 g/mol (potassium salt)
Appearance Yellowish-brown solid
Hazards
GHS labelling:
Pictograms GHS02: FlammableGHS07: Exclamation mark
Signal word Danger
Hazard statements H260, H302, H312, H332
Precautionary statements P223, P231+P232, P280, P301+P312, P302+P352+P312, P304+P340+P312
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Infobox references
Chemical compound

Frémy's salt is a chemical compound with the formula (K42), sometimes written as (K2). It is a bright yellowish-brown solid, but its aqueous solutions are bright violet. The related sodium salt, disodium nitrosodisulfonate (NDS, Na2ON(SO3)2, CAS 29554-37-8) is also referred to as Frémy's salt.

Regardless of the cations, the salts are distinctive because aqueous solutions contain the radical .

Applications

Frémy's salt, being a long-lived free radical, is used as a standard in electron paramagnetic resonance (EPR) spectroscopy, e.g. for quantitation of radicals. Its intense EPR spectrum is dominated by three lines of equal intensity with a spacing of about 13 G (1.3 mT).

The inorganic aminoxyl group is a persistent radical, akin to TEMPO.

It has been used in some oxidation reactions, such as for oxidation of some anilines and phenols allowing polymerization and cross-linking of peptides and peptide-based hydrogels.

It can also be used as a model for peroxyl radicals in studies that examine the antioxidant mechanism of action in a wide range of natural products.

Preparation

Frémy's salt is prepared from hydroxylaminedisulfonic acid. Oxidation of the conjugate base gives the purple dianion:

HON(SO3H)2 → + 2 H
2 + PbO2 → 2 + PbO + H2O

The synthesis can be performed by combining nitrite and bisulfite to give the hydroxylaminedisulfonate. Oxidation is typically conducted at low-temperature, either chemically or by electrolysis.

Other reactions:

HNO2 + 2 HSO
3 → HON(SO
3)
2 + H2O
3 HON(SO
3)
2 + MnO
4 + H → 3 ON(SO
3)
2 + MnO2 + 2 H2O
2 ON(SO
3)
2 + 4 K → K42

History

Frémy's salt was discovered in 1845 by Edmond Frémy (1814–1894). Its use in organic synthesis was popularized by Hans Teuber, such that an oxidation using this salt is called the Teuber reaction.

References

  1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  2. ^ "Synthesis and Characterization of Potassium Nitrosodisulfonate, Frémy's Salt" (PDF). tripod.com.
  3. ^ Wehrli PA, Pigott F (1972). "Oxidation with the nitrosodisulfonate radical. I. Preparation and use of sodium nitrosodisulfonate: trimethyl-p-benzoquinone". Organic Syntheses. 52: 83. doi:10.15227/orgsyn.052.0083.
  4. Wertz JE, Bolton JR (1972). Electron Spin Resonance: Elementary Theory and Practical Applications. New York: McGraw-Hill. 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.
  5. Colacicchi S, Carnicelli V, Gualtieri G, Di Giulio A (2000). "EPR study of Frémy's salt nitroxide reduction by ascorbic acid; influence of bulk pH values". Res. Chem. Intermed. 26 (9): 885–896. doi:10.1163/156856700X00372. S2CID 98775951.
  6. Zielonka J, Zhao H, Xu Y, Kalyanaraman B (October 2005). "Mechanistic similarities between oxidation of hydroethidine by Frémy's salt and superoxide: stopped-flow optical and EPR studies". Free Radical Biology & Medicine. 39 (7): 853–863. doi:10.1016/j.freeradbiomed.2005.05.001. PMID 16140206.
  7. Zimmer H, Lankin DC, Horgan SW (1971). "Oxidations with potassium nitrosodisulfonate (Frémy's radical). Teuber reaction". Chemical Reviews. 71 (2): 229–246. doi:10.1021/cr60270a005.
  8. Islam I, Skibo EB, Dorr RT, Alberts DS (October 1991). "Structure-activity studies of antitumor agents based on pyrrolobenzimidazoles: new reductive alkylating DNA cleaving agents". Journal of Medicinal Chemistry. 34 (10): 2954–2961. doi:10.1021/jm00114a003. PMID 1920349.
  9. ^ Teuber HJ, Benz S (1967). "Reaktionen mit Nitrosodisulfonat, XXXVI. Chinolin-chinone-(5.6) aus 5-Hydroxy-chinolinen". Chem. Ber. (in German). 100 (9): 2918–2929. doi:10.1002/cber.19671000916.
  10. ^ Teuber HJ (1972). "Use of Dipotassium Nitrosodisulfonate (Frémy's Salt): 4,5-Dimethyl-o-Benzoquinone". Org. Synth. 52: 88. doi:10.15227/orgsyn.052.0088.
  11. Xue W, Warshawsky D, Rance M, Jayasimhulu K (2002). "A metabolic activation mechanism of 7H-dibenzocarbozole via o-quinone. Part 1: synthesis of 7H-dibenzocarbozole-3,4-dione and reactions with nucleophiles". Polycyclic Aromatic Compounds. 22 (3–4): 295–300. doi:10.1080/10406630290026957. S2CID 95507636.
  12. Wilchek M, Miron T (March 2015). "Mussel-inspired new approach for polymerization and cross-linking of peptides and proteins containing tyrosines by Frémy's salt oxidation". Bioconjugate Chemistry. 26 (3): 502–510. doi:10.1021/bc5006152. PMID 25692389.
  13. Fichman G, Schneider JP (2021). "Utilizing Frémy's Salt to Increase the Mechanical Rigidity of Supramolecular Peptide-Based Gel Networks". Frontiers in Bioengineering and Biotechnology. 8: 594258. doi:10.3389/fbioe.2020.594258. PMC 7813677. PMID 33469530.
  14. Liu ZL, Han ZX, Chen P, Liu YC (November 1990). "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. 56 (1): 73–80. doi:10.1016/0009-3084(90)90090-E. PMID 1965427.
  15. See:

Further reading

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