Oxone oxidation

Occasionally batches of oxone purchased from Aldrich Chemical Company, Inc., have exhibited reduced reactivity in this oxidation. Oxone exposed to moisture prior to use also gives reduced reactivity in this oxidation. If this occurs oxone is added until oxidation is complete as determined by TLC (Note 9). Potassium carbonate is added as needed to maintain the pH at approximately 9.0. Oxone stored... 

Recently it has been reported that oxidative cleavage of alkenes with catalytic osmium tetroxide is possible in the absence of water using the co-oxidant Oxone (KHSOs). In this case the diol is not formed and the intermediate osmate ester is oxidized by the Oxone and fragments to regenerate osmium tetroxide and release the carbonyl products. For example, the alkene 1-nonene gave octanoic acid (90% yield) under these conditions. 

A convenient newer procedure for preparing various [bis(trifluoroacetoxy)iodo]perfluoroalkanes 37 and also [bis(trifluoroacetoxy)iodo]arenes 38 involves the oxidation of the corresponding aryl and perfluoroalkyl iodides with the commercially available and inexpensive oxidant Oxone (2KHS05-3KHS04-3K2S04) in trifluoroacetic acid at room temperature (Scheme 2.18) [135]. 

Reagents, i, CH Br, NaHMDS ii, Bu Li MgBr2, PhSCH2l, catalytic Li2CuCl oxidant-oxone, MCPBA, or MoO HMPT H20 iii, BuLi, THF, HMPT... 

Use of other nucleophiles in the presence of an oxidant can install other functionality (Scheme 3.55). While N-halosuccinimides are very effective, other systems, such as iodosobenzene diacetate-halide mixtures, or copper(II) halide salts can be employed. The powerful oxidant oxone can also be used in combination with alcohols, to give ethers (Scheme 3.56). Iodine acetate has been used for C-H activation directed by carboxylic acids (Scheme 3.57). The heteroatom may also be supplied intramolecularly (Scheme 3.58). The use of palladium catalysis can also override the inherent regioselectivity of an arene substrate (Scheme 3.59). 

A protocol that sometimes is amenable to scale-up uses as oxidant oxone in aqueous acetone, buffered to pH 7.8-8.0 with sodium bicarbonate [49]. The procedure is mild, cheap and environment-friendly and the oxidation produces sulfoxides or sulfones depending on the equivalents of oxone, temperature and reaction time. When the oxidation is carried out in water only buffered with phosphate to pH 6-7, the reaction is very fast and high conversions of sulfoxides and sulfones are obtained [15]. 

Air Quality Criteria for Oxone and Other Photochemical Oxidants, PubUcation No. EPA-600-8-84-020F, 5 vols., U.S. Environmental Protection Agency, Research Triangle Park, N.C., 1986. EPA pubUshes separate criteria documents for aU the criteria poUutants and they are updated about every five years. 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

The name 5-azaorotic acid should be given to allantoxanic (oxonic) acid but it is not yet commonly used. The elucidation of the correct structure of this compound was closely linked to the solution of the course of oxidation of uric acid mentioned earlier. 

The structure (5) originally proposed by Ponomarev appeared to be confirmed by the conversion of dihydrooxonic acid to allantoin performed by Biltz and Giesler. Biltz and RobP showed later that oxonic acid is identical with allantoxanic acid obtained on oxidation of allantoin. Since that time both these trivial names are in usage. 

Works on the oxidation of uric acid has unequivocally established the triazine structure > ° (9) of oxonic acid. This is further confirmed by the straightforward synthesis described by Piskala and Gut. ° The reaction of biuret (11) with potassium ethyloxalate yielded a potassium salt (24), that with ethyl oxamate, the amide of oxonic acid (25). Both these compounds were converted to 5-azauracil. An analogous reaction with diethyloxalate which should produce an ester of oxonic acid resulted in a mixture of urethane and parabanic acid, however. 

Deactivation (weak) from the adjoining ring does not prevent facile disubstitution of 4-methyl- and 4-phenyl-2,7-dichloro-1,8-naphthyridines wdth alkoxides (65°, 30 min), p-phenetidine (ca. 200°, 2 hr), hydrazine hydrate (100°, 8 hr), or diethylaminoethylmer-captide (in xylene, 145°, 24 hr) mono-substitution has not been reported. Nor does stronger deactivation prevent easy 2-oxonation of 5,7-dimethoxy-l-methylnaphthyridinium iodide wdth alkaline ferricyanide via hydroxide ion attack adjacent to the positive charge and loss of hydride ion by oxidation. 

Tlie reaction of 5,6-dithiabicyclo[2.1.1]hexaiie 11a with OXONE led to the corresponding dithiirane 12a, which was, however, stable only in solution (Amax at 442 nm in CH2CI2). Treatment of the reaction mixture containing 12a with MCPBA gave the dithiirane 1-oxide 13a (8%) (95TL1867). Tire introduction of electron-withdrawing substituents on the benzene rings provided the dithiirane oxide 13b in a better yield (21%). 

Tire reaction of 1,3-dithietanes 14 with OXONE produced dithiirane 1-oxides 15 directly (95TL1867). Dithiirane 1-oxides 15 would be formed through the initially formed 1,3-dithietane oxides. 

Treatment of ethyl 10-methylthio-9-fluoro-3-methyl-2,3-dihydro-7-oxo-7//-pyrido[l,2,3- 7e]-l,4-benzoxazine-6-carboxylate with oxone in aqueous MeOH at 0°C afforded 10-methylsulfonyl derivative (99H(51)1563). Methylthio group in a 7-(4-methylthiophenyl)-5-oxo-2,3-dihydro-5//-pyrido[l,2,3- 7e]-l,4-benzoxazine-3-carboxamide was oxidized to a sulfoxide and a sulfone group (OOMIPl). 

Aiiphadc md aromadc primary amines are rapidly md efficiently oxidized to nitro compounds by dimethyldioxirime. Dimethyldioxirime is prepared by teacdon of OXONE (Du-... 

Primary and secondary aliphatic nitro compounds have been oxidized to aldehydes and ketones, respectively (RR CHN02 RR C=0) with sodium chlorite under phase-transfer conditions, TPAP, Oxone , as well as with other reagents. 

All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyl dioxirane." Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone, various peroxyacids," MeRe03/H202,"" Oxone ," ° tcrt-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds, and sodium perborate." ... 

Dimethyl dioxirane in wet acetone oxidizes isocyanates to nitro compounds (RNCO —> RN02). Oximes can be oxidized to nitro compounds with peroxytri-fluoroacetic acid, or Oxone ," sodiumperborate," among other ways. " Primary and secondary alkyl azides have been converted to nitro compounds by treatment with PhjP followed by ozone. Aromatic nitroso compounds are easily oxidized to nitro compounds by many oxidizing agents. ... 

The regeneration of carbonyl compounds from 1,3-dithianes can be achieved using potassium hydrogen persulfate, Oxone , supported on wet alumina <96SL767> and by periodic acid under non-aqueous conditions <96TL4331>. The deprotection of benzyl substituted 1,3-dithianes can be achieved using the one electron oxidant [Fe(phen)3](PF6)3 <96SL315>. 

This process of aging is believed to be critical in the development of delayed neuropathy, after NTE has been phosphorylated by an OP (see Chapter 10, Section 10.2.4). It is believed that most, if not all, of the B-esterases are sensitive to inhibition by OPs because they, too, have reactive serine at their active sites. It is important to emphasize that the interaction shown in Fignre 2.11 occurs with OPs that contain an oxon group. Phosphorothionates, which contain instead a thion group, do not readily interact in this way. Many OP insecticides are phosphorothionates, but these need to be converted to phosphate (oxon) forms by oxidative desulfuration before inhibition of acetylcholinesterase can proceed to any significant extent (see Section 2.3.2.2). 

Previous studies by Sorokin with iron phthalocyanine catalysts made use of oxone in the oxidation of 2,3,6-trimethylphenol [134]. Here, 4 equiv. KHSO5 were necessary to achieve full conversion. Otherwise, a hexamethyl-biphenol is observed as minor side-product. Covalently supported iron phthalocyanine complexes also showed activity in the oxidation of phenols bearing functional groups (alcohols, double bonds, benzylic, and allylic positions) [135]. Besides, silica-supported iron phthalocyanine catalysts were reported in the synthesis of menadione [136]. 

Wong M-K, T-C Chan, W-Y Chan, W-K Chan, LLP Vrijmoed, DK O Toole, C-M Che (2006) Dioxiranes generated in situ from pyruvates and oxone as environmentally friendly oxidizing agents for disinfection. Environ Sci Technol 40 625-630. 

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