Oxone sulfones

Precautions should be taken to avoid disulfoton loss from stored water, soil, sediment, crop, and vegetable samples (Belisle and Swineford 1988 Miller etal. 1981 Munch and Frebis 1992 Szeto and Brown 1982). Disulfoton, disulfoton sulfone, and disulfoton sulfoxide were not recovered from spiked well water stored 14 days however, sample extracts were stable for 14 days (84-92% recovery) (Munch and Frebis 1992). In most environmental samples, disulfoton will be present along with its environmental transformation products, disulfoton sulfone, disulfoton sulfoxide, disulfoton oxon, disulfoton oxon sulfone, and disulfoton oxon sulfoxide (Szeto and Brown 1982). Disulfoton and its oxon are very unstable, and they oxidize rapidly to the corresponding sulfoxides. The sulfoxides are relatively stable, but they oxidize slowly to their sulfones, which are most stable (Szeto and Brown 1982). Several methods for determining the metabolites of disulfoton in environmental samples are included in Table 6-2. 

Dipyridone, see Diquat Disacryl, see Acrolein Disulfoton oxon sulfone, see Disulfoton Disulfoton oxon sulfoxide, see Disulfoton Disulfoton sulfone, see Disulfoton Disulfoton sulfoxide, see Disulfoton 2,2 -Dithiobis-ethanol, see Phorate Dithiophosphoric acid, see Phorate... 

Thiadiazuron Phorate oxon, see Phorate Phorate oxon sulfone, see Phorate Phorate oxon sulfoxide, see Phorate Phorate sulfone, see Phorate Phorate sulfoxide, see Phorate Phoratoxon sulfone, see Phorate Phoratoxon sulfoxide, see Phorate Phosalone oxon, see Phosalone Phosgene, see p-BHC, Carbon tetrachloride. 

Disulfoton was translocated from a sandy loam soil into asparagus tips. Disulfoton sulfoxide, disulfoton sulfone, disulfoton oxon sulfoxide, and disulfoton oxon sulfone were recovered as metabolites (Szeto and Brown, 1982 Szeto et al., 1983). Disulfoton sulfoxide and disulfoton sulfone were also identified in spinach plants 5.5 months after application (Menzer and Dittman, 1968). Menzer et al. (1970) reported that degradation of disulfoton in soil degraded at a higher rate in the winter months than in the summer months. They postulated that soil type, rather than temperature, had a greater influence on the rate of decomposition of disulfoton. Soils used in the winter and summer months were an Evesboro loamy sand and Chillum silt loam, respectively. The half-life in soil is approximately 5 d (Jury et al., 1987). 

Plant. Oat plants were grown in two soils treated with [ Ciphorate. Most of the residues remained bound to the soil. Less than 2% of the applied [ Ciphorate was recovered from the oat leaves. The major residues in soil were phorate and the corresponding oxon, sulfone, oxon sulfone, sulfoxide, and oxon sulfoxide (Fuhremann and Lichtenstein, 1980). These compounds were also found in asparagus tissue and soil treated with the insecticide (Szeto and Brown, 1982). 

Plant. Oat plants were grown in two soils treated with [ Cjphorate. Most of the residues remained bound to the soil Less than 2% of the applied [ Cjphorate was recovered fi om the oat leaves. The major residues in soil were phorate and the corresponding oxon, sulfone, oxon sulfone, sulfoxide and oxon sulfoxide (Fuhretnatm and Lichtenstein, 1980). These compounds were also found in asparagus tissue and soil treated with the insecticide (Szeto and Brown, 1982). In soil and plants, phorate is oxidized to the corresponding sulfone which is further oxidized to the sulfoxide (Metcalf et al., 1957 Fukuto and Metcalf, 1969 Getzin and Shanks, 1970). Both metabolites were identified in spinach 5.5 months after application (Menzer and Dittman, 1968). The half-lives in coastal Bermuda grass and alfalfa are 1.4 (Leuck and Bowman, 1970) and 3.6 days (Dobson et al., 1960), respectively. 

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). 

B. Fluoromethyl phenyl sulfone (2). To a 3-L, three-necked, round-bottomed flask, equipped with an overhead stirrer, thermometer, and 1-L addition funnel with sidearm are added Oxone (221.0 g, 0.36 mol) (Note 9) and water (700 mL). The mixture is cooled to 5°C and a solution of the crude fluoromethyl phenyl sulfide (1) in methanol (700 mL) is placed in the addition funnel and added in a slow stream to the stirring slurry. After addition of the sulfide, the reaction mixture is stirred at room temperature for 4 hr, (Note 10) and the methanol is removed on a rotary evaporator at 40°C. The remaining solution is extracted with methylene chloride (2 x 500 mL). The combined organic layers are dried over magnesium sulfate, concentrated to ca. 150 mL, filtered through a plug of silica gel (230-400 mesh, 300 mL, 10 x 6.5 cm), and washed with an additional 500 mL of methylene chloride (Note 11). The colorless filtrate is concentrated and the resulting oil or solid is dried under vacuum (0.1 mm) at room temperature to provide 29 g of crude fluoromethyl phenyl sulfone (2) as a solid... 

For the synthesis of the title compound, Oxone or 3-chloroperbenzoic acid2 can be used to oxidize the sulfide to the sulfone. The title compound is a key reagent for the preparation of fluoroalkenes from aromatic11 and aliphatic2 aldehydes. Recently, a stereospecific method to (E)- and (Z)-fluoroalkenes was reported using this reagant.12 13 14... 

Methidathion oxon, see Methldathion Methiocarb sulfone, see Methlocarb Methiocarb sulfoxide, see Methiocarb Methionine, see Thiram Methoxyacetaldehyde, see Alachlor Methoxyacetic acid, see 1,4-Dioxane p-Methoxybenzaldehyde, see Methoxychlor p-Methoxybenzoic acid, see Methoxychlor... 

Kennedy and Stock reported the first use of Oxone for many common oxidation reactions such as formation of benzoic acid from toluene and of benzaldehyde, of ben-zophenone from diphenyhnethane, of frawi-cyclohexanediol Ifom cyclohexene, of acetone from 2-propanol, of hydroquinone from phenol, of e-caprolactone from cyclohexanone, of pyrocatechol from salicylaldehyde, of p-dinitrosobenzene from p-phenylenediamine, of phenylacetic acid from 2-phenethylamine, of dodecylsulfonic acid from dodecyl mercaptan, of diphenyl sulfone from diphenyl sulfide, of triphenylphosphine oxide from triphenylphosphine, of iodoxy benzene from iodobenzene, of benzyl chloride from toluene using NaCl and Oxone and bromination of 2-octene using KBr and Oxone . Thus, they... 

It has been shown that a phase-transfer catalyst could control the oxidation of sulfide to the corresponding sulfoxide. Thus, the oxidation of diaryl sulfides to sulfoxides using Oxone and PTC (equation 54) is in contrast with the reaction in polar solvents without PTC which gives sulfones as a major product. 

Aromatic sulfides can be selectively converted into sulfoxides or sulfones by using Oxone under solid state conditions or with buffered Oxone in acetonitrile or acetone . 

Oxidation of sulfides and sulfoxides using Oxone dispersed on silica gel or alumina was reported . A study of surface mediated reactivity of Oxone compared its reactivity with that of ferf-butyl hydroperoxide. Oxidation of sulfides to sulfones in aprotic solvents mediated by Oxone on wet montmorillonite or clay minerals proceeds in high yields. Interestingly, when Oxone on alumina is applied for selective oxidation of sulfides in aprotic solvents, the product distribution is temperature-dependent and sulfoxides or sulfones are obtained in good to excellent yields (equation 56) . ... 

Sulfides in the electrophilic positions are often oxidized to sulfones to facilitate nucleophilic displacement reactions. The sulfoxide is initially formed, and can sometimes be isolated, but normally the oxidation is allowed to proceed fully to give the sulfone. Peroxyacids are commonly used as the oxidant, although other reagents such as oxone (potassium peroxymonosulfate) can also be employed <20030L1011, 2006ARK(vii)452>. 

Sulfoxides and sulfones can be prepared on cross-linked polystyrene by oxidation of thioethers. The most commonly used reagent for this purpose is MCPBA in DCM [8,12,32,57,80-82] or dioxane [50,83] (Table 8.6), but other oxidants such as H2O2 in acetic acid [34], oxone (Entry 7, Table 8.6), or oxaziridines [84] have also been used. PEG-bound thioethers have been converted into sulfones by oxidation with MCPBA in DCM [52,54] or with Os04/NMO [85], The oxidation of thioethers to sulfoxides requires careful control of the reaction conditions to prevent the formation of sulfones. Sulfones have also been prepared by S-alkylation of polystyrene-bound sulfi-nates (Entries 8 and 9, Table 8.6), by a-alkylation of sulfones (BuLi, THF, alkyl halide [86]), and by addition of sulfinyl radicals to resin-bound alkenes or alkynes (Entry 11, Table 8.6). 

Both isomeric forms of (+)- and (—)-(camphorylsulfonyl)oxaziridines are available by oxidation of the corresponding sulfonimines with buffered potassium peroxymonosulfate (oxone). Since oxidation can only take place from the endo-fa.ce of the C=N double bond due to steric blocking of the exo-face, a single oxaziridine isomer is obtained. The enantiomerically pure sulfonimines can be prepared in three steps in better than 80% yield from inexpensive (+)- and (—)-camphor-10-sulfonic acids. Alternatively they are commercially available200. 

Oxaziridines, 276, 277 2-Oxazolidones, chiral, 379-381 2-Oxazoline-5-ones, 151 Oxazolines, 147, 265, 588 Oxime sulfonates, 245-246 jx-Oxobis(chlorotriphenylbismuth), 381-382 Oxodiperoxymolybdenum(pyridine)(hexamethyl phosphoric triamide), 382-383 p,3-Oxohexakis( x-triinethylacetato)trimethanol-triiron(ffl), 382-383 a-Oxoketene dithioacetals, 185 Oxomethoxymolybdenum(V) 5,10,15,20-totraphcnylpoiphyrin, 383 Oxone, 442 Oxosulfenylation, 205... 

Figure 6. Dissipation of chlorthiophos its sulfoxide (A), and its sulfone (0), and chlorthiophos oxon sulfoxide (/S) after an application of 0.8 lb AI chlorthiophos/100 gal of spray on lemons (6).

In the reaction of Oxone with l-substituted-l//-5-alkylsulfanyltetrazoles 436, the yield of the corresponding sulfone 437 depends on the structure of the substituent attached to sulfur. For instance, 5-( -butyl)sulfanyl-l-(/-butyl)tetrazole with Oxone in methanol gave the corresponding sulfone in 81% yield, whereas the oxidation of 5-benzylsulfanyl-l-(/-butyl)tetrazole formed only 12% of the sulfone <2000SL365>. 

The epoxide formation is thought to proceed via Oxone-mediated dioxirane formation and inclusion of the aromatic moiety inside the cavity. The influence of the substrate binding inside the CD cavity was evaluated by inhibitory experiments with naphthalene-2-sulfonate, which is known to bind both a- and / -CD with good affinity. As expected, the addition of 2 equivalents of inhibitor to the reaction mixture resulted in a significant decrease in reaction rate. 

Catalytic oxidation of RtS to R S = 0.2 This sulfonamide can function as a catalyst for oxidation of sulfides selectively to sulfoxides by Oxone (potassium peroxymonosulfate). The net effect involves transfer of oxygen from an N-sulfon-yloxaziridine to the sulfide. This catalytic system is useful because sulfones are formed if at all only in traces. 

The desilylated products 31 and 32 (Scheme 20) were obtained by the protiodesilylation of a number of thioacylsilane adducts and the corresponding sulfones obtained by oxidation of the cycloadducts with oxone (potassium hydrogen persulfate). Compounds 31 are formally derived from unstable thioaldehydes and the cyclic sulfones 32 from thioaldehyde 5,5-dioxide (sulfenes) (Scheme 20). It should be noted that sulfenes produced by dehydrochlorination... 

A number of other oxidants which produce sulfones from sulfoxides are known, such as N02BF4, ° oxygen with Ir or Rh catalysts, ozone,KHSOs (Oxone) and K2S20s. Oxone is a highly chemoselective oxidant for the conversion of sulfides to sulfones without affecting hydroxy or al-kenic groups (equation 37). Similarly flavin (14) oxidizes aryl methyl sulfoxides to sulfones fairly selectively. ... 

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