Oxone

The triple salt is produced via peroxysulfuric acid, which is generated in situ from sulfuric acid (oleum) and hydrogen peroxide and with potassium hydroxide.^[4] X-ray crystallography confirms the triple salt formulation, revealing hydrogen-bonding network that entraps the persulfate anion. The O-O distance is 1.458(2) Å, as found in H₂O₂.^[5]

The purity of Oxone can be determined by iodometric titration. Heavy metal salts catalyze the decomposition of the title compound, based on reporting on its triple salt formulation.^[3] An estimated 43-45% of it, by weight, of which 5.2% active oxygen is theoretically possible, and 4.7% was typically observed.^[6] In 2012, a review was reporting the KHSO₅ estimate to be "about 50% per mole" of triple salt.^[3]) The stability advantage notwithstanding (see following), methods were developed to deliver a forms of the title compound that required smaller amounts in reactions, and this was achieved on large scale in 2002 via preparations of purified KHSO₅·H₂O.^{[3][7][needs update]}

Underlying the uses of Oxone is the highly positive oxidation potential for peroxymonosulfate, which is +1.81 V.

Preparative chemistry

Oxone is a versatile oxidant in organic chemistry.^[14][3][15] It oxidizes terminal alkenes to epoxides. It converts internal alkenes into two equivalents of carboxylic acid. Oxone convert aldehydes to carboxylic acids. When such reactions are conducted in the presence of alcoholic solvents, the corresponding esters may be obtained.^[16]

Oxone converts ketones to dioxiranes, which can be used for diverse oxidations in organic synthesis.^[17] and in the oxidation of other unsaturated functionalities, heteroatoms, and even some alkane C-H bonds.^[18]

Oxone is used in the production of some organic periodinanes, notably the oxidation of 2-iodobenzoic acid to 2-iodoxybenzoic acid (IBX).^{[19][non-primary source needed]}

Peroxymonosulfate-driven conversions can be used with sulfides and selenides to prepare sulfones and selenones, with anilines and amino sugars to provide nitro compounds, oximes to provide nitro compounds (in aqueous buffered conditions) or to return the parent carbonyl compounds (in the presence of alumina, with microwave heating), primary and secondary amines to provide hydroxylamines (using adsorbed Oxone) or N-nitrosation products (in the presence of sodium nitrite), pyridines and tertiary amines to provide amine oxides, and phosphorus(III) compounds to provide phosphono-compounds largely retaining configuration at phosphorus (with comparable outcomes when a sulfur or selenium atom replaces the phosphorus(III) lone pair).^[3]

Examples of preparative scale oxidatives of these types are the conversion of an acridine derivative to the corresponding acridine-N-oxide,^[20] and the synthesis of fluoromethyl phenyl sulfone, a reagent used in the synthesis of fluoroalkenes.^[21]

• Wu, Mingsong; Xu, Xinyang; Xu, Xun (November 2014). "Algicidal and Bactericidal Effect of Potassium Monopersulfate Compound on Eutrophic Water". Applied Mechanics and Materials. 707: 259. doi:10.4028/www.scientific.net/AMM.707.259. S2CID 98000605. Retrieved 3 November 2025.^{[non-primary source needed][better source needed]}

• Crandall, Jack K.; Shi, Yian; Burke, Christopher P.; Buckley, Benjamin R. (14 September 2012) [2001]. Paquette, Leo A. (ed.). Encyclopedia of Reagents for Organic Synthesis. New York, NY: Wiley & Sons. doi:10.1002/047084289x.rp246.pub3. ISBN 9780470842898. Retrieved 3 November 2025. The original 1995 print publication of this chapter by Crandall was vol. 3, on pages 295ff.

• DuPont Staff (2008). "DuPont™ Oxone® Monopersulfate Compound / General Technical Attributes" (PDF). du Pont de Nemours. Wilmington, DE: E.I. du Pont de Nemours & Co. Retrieved 3 November 2025 – via Ataman Kimya A.Ş.(AtamanKimya.com).

• Jakob, Harald; Leininger, Stefan; Lehmann, Thomas; Jacobi, Sylvia & Gutewort, Sven (15 July 2007). "Peroxo Compounds, Inorganic". In Ley, Claudia (ed.). Ullmann's Encyclopedia of Industrial Chemistry. Weinheim, Germany: Wiley-VCH. doi:10.1002/14356007.a19_177.pub2. ISBN 978-3-527-30673-2. Retrieved 3 November 2025.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)

• Mundy, B.P.; Ellerd, M.G. & Favaloro Jr., F.G. (2005). "Oxone®". Name Reactions and Reagents in Organic Synthesis (2nd ed.). Hoboken, NJ: John Wiley & Sons. p. 828. ISBN 9780471739869. Retrieved 3 November 2025.{{cite book}}: CS1 maint: multiple names: authors list (link)

• Page, P.C.B.; Barros, D.; Buckley, B.R.; Ardakani, A. & Marples, B.A. (2004). "Organocatalysis of Asymmetric Epoxidation Mediated by Iminium Salts under Nonaqueous Conditions". J. Org. Chem. 69 (10): 3595–3597. doi:10.1021/jo035820j. PMID 15132582. Retrieved 3 November 2025.{{cite journal}}: CS1 maint: multiple names: authors list (link) Presents an organic-soluble form of Oxone®, tetraphenylphosphonium peroxymonosulfate (Ph₄PHSO₅), and its successful deployment in the asymmetric epoxidation using peroxymonosulfate-generated oxaziridinium salts.

• Travis, B. R.; Ciaramitaro, B. P. & Borhan, B. (30 September 2002). "Preparation of Purified KHSO₅·H₂O and nBu₄NHSO₅ from Oxone by Simple and Efficient Methods". Eur. J. Org. Chem.: 3429–3434. doi:10.1002/1099-0690(200210)2002:20<3429::AID-EJOC3429>3.0.CO;2-D. Retrieved 3 November 2025.{{cite journal}}: CS1 maint: multiple names: authors list (link) The article has been made available by an author, at this link.