Triple salts

Peroxomonosulfa.tes, When oleum is mixed with hydrogen peroxide and the mixture is partially neutralized by potassium hydroxide, a triple salt [37222-66-5] crystallizes out. In the old nomenclature, the formula for the triple salt was written as if it comprised three salts 2... 

In general, peroxomonosulfates have fewer uses in organic chemistry than peroxodisulfates. However, the triple salt is used for oxidizing ketones (qv) to dioxiranes (7) (71,72), which in turn are useful oxidants in organic chemistry. Acetone in water is oxidized by triple salt to dimethyldioxirane, which in turn oxidizes alkenes to epoxides, polycycHc aromatic hydrocarbons to oxides and diones, amines to nitro compounds, sulfides to sulfoxides, phosphines to phosphine oxides, and alkanes to alcohols or carbonyl compounds. 

No toxicological studies have been reported on the triple salt. However, because of the common confusion of this compound with potassium hydrogen monoperoxosulfate monohydrate, it is possible that the pubHshed descriptions of the toxic properties of this latter compound actually refer to the triple salt. If this is so, then the triple salt must be regarded as toxic and irritating to skin, eyes, and mucous membranes (2). 

The triple salt is classified by the UN not as an oxidizer but as a corrosive, and thus must be transported under the UN No. 1759 for corrosive soHds NOS. It should be kept away from combustible material. 

The triple salt is better known by the trademarks Caroat (Degussa), OXONE Monopersulfate Compound (Du Pont), and Curox (Laporte). It is also known as potassium caroate. It has been made on a commercial scale siace the 1950s, and the world market ia 1994 was several thousand tons. It is made commercially by Peroxid-Chemie (Germany), Degussa (Germany), Du Pont (United States), and Migas (Japan). In 1994, the United Kingdom price was J1.80/kg ( 2.67/kg). 

Potassium hydrogen monoperoxosulfate monohydrate [14696-73-2] KHSO 20, related to the triple salt, is not made commercially. The crystal stmcture has been determined and some features of its Raman and ir spectra recorded (69). This compound is more stable under x-rays than the triple salt. The 0—0 distance is 0.1460 nm. The dihedral angle of the 0—0 moiety is about 90°, similar to that ia soHd hydrogea peroxide. This compouad is reported as toxic and irritating to eyes, skin, and mucous membranes (2). Although undoubtedly correct, this description probably better relates to the triple salt. 

Oxidation of Chlorides. Hypochlorite can also be formed by the in situ oxidation of chloride ions by potassium peroxymonosulfate [25482-78-4] (36). Ketones like acetone cataly2e the reaction (37). The triple salt of potassium peroxymonosulfate is a stable powder that has been combiaed with chloride salts and sold as toilet bowl cleaners. Bromides can be used ia place of chlorides to form hypobromites, and such combiaations are used to disiafect spas and hot tubs. 

Chlorination of lime slurried in strong NaOCl solution, followed by cooling to — 15°C, precipitates about 80% of the av CI2 as large hexagonal crystals of a triple salt Ca(OCl)2 NaOCl NaCl -12H20 [64147-46-2] (182). The recovered triple salt, free of much of the lime impurities, is treated with chlorinated lime slurry to produce neutral calcium hypochlorite dihydrate crystals [22464-76-2]. 

Commercial Processes. Olin s earlier triple salt process, originally commercialized in 1928, was modified in 1983. In the patented process, a slurry of dibasic calcium hypochlorite is mixed with a strong, low salt sodium hypochlorite solution and hypochlorite Hquors and chlorinated. The resultant Ca(OCl)2 2H20 slurry is filtered, the cake going to the dry-end and the filtrate to the dibasic precipitation step where it reacts with lime. 

Drilling, m. triplet (Mach.) lantern, -salz, n. triple salt. 

Tripel-erde, /. tripoli. -phosphat, n. triple phospate. -punkt, m. triple point, -salz, n, triple salt, stein, m. tripoli ston4 ... 

Reactive oximes and their salts, such as potassium 2,3-butanedione monoximate found in commercially available RSDL, are extremely effective at rapidly detoxifying nerve agents. Some chloroisocyanurates, similar to those found in the CASCAD, are effective at detoxifying V-series agents and so is oxone, a peroxymonosulfate triple salt. 

Matsushita et al. (2007) synthesized a genuine organic paramagnetic conductor. Electrocrystallization of the thia-selena compound bearing an A -oxyl leads to a perchlorate triple salt, which displays as magnetism as electric conductivity (see Scheme 8.15). 

Dimethyldioxirane is a powerful oxidant prepared by reacting acetone with KHSOs the latter is commercially available as a triple salt under the trade name of oxone. 1,4-Dinitrocubane... 

Oxone is a registered trademark of DuPont with potassium peroxymonosulfate KHSOs (potassium monopersulfate) as oxidizing ingredient of a triple salt with the formula... 

The synthetically most useful method for the preparation of dioxiranes is the reaction of appropriate ketones (acetone, trill uoroacetone, 2-butanone, cyclohexanone etc.) with Caroate, commercially available as the triple salt of potassium monoperoxysul-fate (KHSOs). The catalytic cycle of the dioxirane formation and oxidation is shown in Scheme 1 in general form. For acetone as the ketone, by simple distillation at a slightly reduced pressure ca 100 torr) at room temperature ca 20 °C), Jeyaraman and Murray successfully isolated dimethyldioxirane (DMD) as a pale yellow solution in acetone (maximally ca 0.1 M). This pivotal achievement in 1985 fomented the subsequent intensive research activity in dioxirane chemistry, mainly the synthetic applications but also the mechanistic and theoretical aspects. The more reactive (up to a thousandfold ) fluorinated dioxirane, methyl(trifluoromethyl)dioxirane (TFD), was later isolated in a similar manner by Curd, Mello and coworkers". For dioxirane derived from less volatile ketones, e.g. cyclohexanone, the salting-out technique has been developed by Murray and coworkers to obtain the corresponding dioxirane solution. 

Figure 19.8 (a) Structure of native CI2 plus four simulated transition states for unfolding. [From A. J. Li and V. Daggett, Proc. Natl. Acad. Sci. USA 91,10430 (1994) A. J. Li and V. Daggett, l Molec. Biol. 257,412 (1996)). (b) Residues Lys-2, Glu-7, and Asp-23 form a triple salt bridge in the native structure (right) that is broken in the simulated transition states for the unfolding (left). 

In general, peroxomonosulfates have fewer uses in organic chemistry Uian peroxodisulfates. However, the triple salt is used for oxidizing ketones to dioxiianes, which in turn me useful oxidants in oiganic chemistry... 

Potassium hydrogen monoperoxosulfate monohydrate KHSO5 H2O, related to the triple salt, is not made commercially. This compound is reported as toxic and irritating to eves, skin, and mucous membranes. Although undoubtedly correct this description probably better relates to the triple salt. 

C. Przibylla prepared the triple salt ammonium copper lead nitrite,... 

---