Frémy's salt
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| Names | |
|---|---|
| IUPAC name
Potassium nitrosodisulfonate | |
| Identifiers | |
| 14293-70-0 | |
| ECHA InfoCard | 100.034.729 |
| PubChem | 3032624 |
| Properties | |
| K2NO(SO3)2 | |
| Molar mass | 268.33 g/mol (potassium salt) |
| Hazards | |
| Main hazards | Harmful (Xn) |
| R-phrases | R14 R20/21/22 |
| S-phrases | S36 |
| Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| Infobox references | |
Frémy's salt, discovered in 1845 by Edmond Frémy (1814–1894),[1] is a chemical compound and a strong oxidizing agent. The formal name is disodium nitrosodisulfonate or Na2NO(SO3)2, but the expression "Frémy's salt" refers equally well to potassium nitrosodisulfonate, also known as potassium peroxylamine disulfonate. Frémy’s salt (chemical formula: (K4[ON(SO3)2]2) is commonly known as potassium nitrodisulfonate radical dianion (NDS) and potassium peroxylamine disulfonate (K2[NO(SO3)2]). NDS, a product of disassociation of Frémy’s salt, is commonly used to examine the mechanism of oxidation and hydroxylation.[2] Frémy’s salt is a commercially accessible dimer of NDS, it is also a relatively stable source of water-soluble nitroxyl radical that is used as an electronic spin resonance (ESR) standard for g-value determination and radical quantization it is also mainly used in oxidation reactions.[3][4] Impurities, which may or may not be present in commercial samples, can catalyze the explosive decomposition reaction of this compound in the presence of oxygen.
Applications
The nitroso compound is a persistent radical like TEMPO. It is especially useful in oxidations of anilines and phenols to quinones.[5][6]
Fremy's salt, being a long-lived free radical, is a useful reagent for electron paramagnetic resonance (EPR) work. The molecule gives an intense EPR spectrum dominated by three lines of equal intensity with a spacing of about 13 G (= 1.3 mT). For more details, see Wertz and Bolton (1972).[7]
Fremy’s salt is commonly used in oxidation of aromatic amine and phenol structures.[2][8] 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.[9][10] Also are used in the synthesis of metabolites which are found to later bind with DNA.[11] One of its few biological applications involves evaluation of radical scavenging activity and EPR kinetic studies.[12] It is also a useful tool in understanding the reduction mechanism by ascorbic acid (AscH2).[11]
Preparation
Fremy's salt is commercially available. It can be prepared by the addition of sodium nitrite, sodium bicarbonate, and sulfur dioxide to disodium hydroxylaminedisulfonate and carbon dioxide followed by one-electron oxidation by electrolysis in a basic solution.[13] This reaction must be carried at 5˚C or lower with constant stirring.[14]
Other Reactions:
- HNO2 + 2 HSO3− → HON(SO3)22− + H2O
- 3 HON(SO3)22− + MnO4− + H+ → 3 ON(SO3)22− + MnO2(s) + 2 H2O
- 2 ON(SO3)22− + 4 K+ → K4[ON(SO3)2]2(s)
In the solid phase, potassium nitrodisulfonate has a bright yellowish-brown color, but it is bright violet in aqueous solutions.[14] EPR measurements can be made to ensure the purity and paramagnetism of the compound.
References
- ↑ See:
- Frémy, E. (1845) "Sur un nouvelle série d'acides formés d'oxygène, de soufre, d'hydrogène et de d'azote" (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, 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" (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.
- "Séances académiques," L'Institut, no. 619, 12 November 1845, pp. 393. Here a committee of the French Academy of Sciences reviewed Frémy's findings.
- Edward Divers and Tamemasa Haga (1900) "Identification and constitution of Fremy's sulphazotised salts of potassium," Journal of the Chemical Society, Transactions, 77 : 440-446. Here, correct formulae for Frémy's salts are presented. On p. 445, the salt that Frémy called sulfazidate is identified as ON(SO3K)2.
- 1 2 Zielonka, Jacek; et al. (2005). "Mechanistic similarities between oxidation of hydroethidine by Fremy'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.
- ↑ Weil, J. A.; Bolton, J. R.; Wertz, J. E. (1994). "Electron paramagnetic resonance: elementary theory and practical applications". Org. Synth.
- ↑ Zielonka, Jacek; et al. (2005). "Mechanistic similarities between oxidation of hydroethidine by Fremy'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.
- ↑ See, for example, Islam, Imadul Islam; Skibo, Edward B.; Dorr, Robert T.; Alberts, David S. (1991). "Structure-activity studies of antitumor agents based on pyrrolo[1,2-a]benzimidazoles: new reductive alkylating DNA cleaving agents". Journal of Medicinal Chemistry. 34 (10): 2954–2961. doi:10.1021/jm00114a003. PMID 1920349.
- ↑ Teuber, Hans-J.; Benz, Siegfried (1967). "Reaktionen mit Nitrosodisulfonat, XXXVI. Chinolin-chinone-(5.6) aus 5-Hydroxy-chinolinen". Chem. Ber. 100 (9): 2918–29. doi:10.1002/cber.19671000916. Abstract (in German).
Teuber, Hans-J. (1972). "Use of dipotassium nitrosodisulfonate (Fremy's salt): 4,5-dimethyl-o-benzoquinone". Org. Synth. 52: 88.; Coll. Vol., 6, p. 480 - ↑ Wertz, J. E.; Bolton, J. R. (1972). Electron Spin Resonance: Elementary Theory and Practical Applications. New York: McGraw-Hill. ISBN 0-07-069454-0. - See page 463 for information on intensity measurements and page 86 for an EPR spectrum of Fremy's salt.
- ↑ W. Xue et al. (2002). "A metabolic activation mechanism of 7H-dibenzo[C,G]carbozole via 0-quinon. Part 1: synthesis of 7H-dibenzo[C,G]carbozole-3,4-dione and reactions with nucleophiles". Org. Synth. 22: 295–300.
- ↑ Liu, Z.-L.; Han, Z.-X.; Chen, P.; Liu, Y.-C (1990). "Stopped-flow ESR study on the reactivity of vitamin E, vitamin C and its lipophilic derivatives towards Fremy's salt in miceller systems". Chem. Phys. Lipids. 56 (1): 73–80. doi:10.1016/0009-3084(90)90090-E. PMID 1965427.
- ↑ Z.L., Liu, Z.X. Han, P. Chen and Y.C. Liu (1990). "Chem. Phys. Lipid". 56: 73.
- 1 2 W. Xue; et al. (2002). "A metabolic activation mechanism of 7H-dibenzo[C,G]carbozole via 0-quinon. Part 1: synthesis of 7H-dibenzo[C,G]carbozole-3,4-dione and reactions with nucleophiles". Polycyclic Aromatic Compounds. 22 (3): 295–300. doi:10.1080/10406630213597.
- ↑ Di Giulio; et al. (2000). "EPR study of Fremy's salt nitroxide reduction by ascorbic acid; influence of bulk pH values". Res. Chem. Intermed. 26 (9): 885–896. doi:10.1163/156856700X00372.
- ↑ Wehrli, Pius A.; Pigott, Foster (1972). "Oxidation with the nitrosodisulfonate radical. I. Preparation and use of sodium nitrosodisulfonate: trimethyl-p-benzoquinone". Org. Synth. 52: 83.; Coll. Vol., 6, p. 1010
- 1 2 http://chemistris.tripod.com/science/synthesis_of_fremys_salt.pdf
Further reading
- Morey, J. (1988). "Undergraduate Experiments with a Long-Lived Radical (Fremy's salt): Synthesis of 1,4-Benzoquinones by Degradative Oxidation of p-Hydroxybenzyl Alcohols". J. Chem. Ed. 65 (7): 627–629. doi:10.1021/ed065p627.