Disulfones oxidation

Hacherl, E.L. et al.. Measurement of iron (III) bioavailability in pure iron oxide minerals and soils using anthraquione-2,6-disulfonate oxidation. Emiron. Sci. Technoi, 35. 4886, 2001. 

Sulfonates with ether linkages include ring-sulfonated alkylphenol ethoxylates and a disulfonated alkyldiphenyl oxide, Dowfax 2A1, and 3B2 (Dow Chemical Company). This surfactant is characterized by high solubiUty in salt solutions, strong acids, or bases. It is used in industrial and institutional cleaners. 

Allied-Signal Process. Cyclohexanone [108-94-1] is produced in 98% yield at 95% conversion by liquid-phase catal57tic hydrogenation of phenol. Hydroxylamine sulfate is produced in aqueous solution by the conventional Raschig process, wherein NO from the catalytic air oxidation of ammonia is absorbed in ammonium carbonate solution as ammonium nitrite (eq. 1). The latter is reduced with sulfur dioxide to hydroxylamine disulfonate (eq. 2), which is hydrolyzed to acidic hydroxylamine sulfate solution (eq. 3). 

DihydroxyanthraquiQone (anthranifin) [117-12-4] (47) is an important iatermediate for manufacturiag disperse blue dyes, eg. Cl Disperse Blue 73 (113), and is prepared from anthraquiQone-l,5-disulfonic acid by heating with an aqueous suspension of calcium oxide and magnesium chloride under pressure at 200—250°C (67). Alternative methods have been proposed, ie, direct replacement of the NO2 groups of 1,5-dinitroanthraquiaone (49) (68) or the route via 1,5-dimethoxyanthraquiaone [6448-90-4] (48) and subsequent hydrolysis (69). 

Juglone is most readily synthesized by Bemthsen s method. However, this method is too drastic and results in low yields (56). Somewhat better yields are obtained by using Fremy s salt (potassium nitroso disulfonate) as the oxidant (57). By using thallium trinitrate to oxidize 1,5-dihydroxynaphthalene, yields as high as 70% of juglone have been reported (58). 

NMR and, 3, 951 aromaticity, 3, 945 delocalization energy, 3, 959 deprotonation, 3, 972 disulfones reactions, 3, 970 double bond character, 3, 945 electronic energy levels, 3, 946 electrophilic reactions, 3, 965 electrophilic substitution, 3, 960 half-wave potential, 3, 968 NMR, 3, 952 H NMR, 3, 951 nucleophilic reactions, 3, 969 oxidation, 3, 967 oxides... 

An example of a process using O2 to oxidize HiS is the Stretford process, which is licensed by the British Gas Corporation. In this process the gas stream is washed with an aqueous solution of sodium carbonate, sodium vanadate, and anthraquinone disulfonic acid. Figure 7-9 shows a simplified process diagram of the process. 

The conversion of cyclic sulfides to sulfones is accompbshed by more energetic oxidations. Perhalogenated thiolanes [106] and 1,3-dithietanes [107] are oxidized to sulfones and disulfones, respectively, by a mixture of chromium trioxide and nitric acid (equation 98) The same reagent converts 2,4-dichloro-2,4-bis(tnfluoromethyl)-l,3-dif/u cto cs to disulfone derivatives [107], whereas trifluoromethaneperoxysulfonic acid converts the starting compound to a sul-fone-sulfoxide derivative [2(equation 99). 

Oxidation of hydroxylamine A, A -disulfonate with permanganate or Pb02 yields the intriguing... 

Unique methods based on new principles have been developed within the past 10 years. Threonine (27,28,249) is oxidized by lead tetraacetate or periodic acid to acetaldehyde, which is determined by photometric analysis of its p-hydroxydiphenyl complex or iodometric titration of its combined bisulfite. Serine is oxidized similarly to formaldehyde, which is determined gravimetrically (207) as its dimedon (5,5-dimethyldihydro-resorcinol) derivative or photometric analysis (31) of the complex formed with Eegriwe s reagent (l,8-dihydroxynaphthalene-3,5-disulfonic acid). It appears that the data obtained for threonine and serine in various proteins by these oxidation procedures are reasonably accurate. [Block and Bolling (26) have given data on the threonine and serine content of various proteins. ]... 

Anhydride and sulfone formation are not the only side reactions. Other side reactions lead to colored products (excess S03, high temperatures), traces of disulfonic acid, olefins, and oxidation products. 

Because of disulfonation and oxidation reactions, an excess of S03 must be used. Operating conditions for a-olefin sulfonation are as follows ... 

Abbreviations DEPC, diethylpyrocarbonate DCCD, Af.iV -dicyclohexylcarbodiimide EEDQ, N-ethyoxycarbonyl-2-ethoxy-1,2-dihydroquinoline NEM, A-ethylmaleimide PAO, phenylarsine oxide NPM, IV-phenylmaleimide PLP, pyridoxal phosphate DIDS, diisothiocyanostilbene disulfonate PITC, phenylisothiocyanate. 

Bacteria have been isolated using reduced anthraquinone-2,6-disulfonate (HjAQDS) as electron donor and nitrate as electron acceptor (Coates et al. 2002). The organisms belonged to the a-, p-, y-, and 5-subdivision of the Proteobacteria, and were able to couple the oxidation of H AQDS to the reduction of nitrate with acetate as the carbon source. In addition, a number of C2 and C3 substrates could be used including propionate, butyrate, fumarate, lactate, citrate, and pyruvate. 

Diazonium salts react with bis(methylsulfonyl) methane (107) (X = S02CH3) to yield a 1,3-diaryl tetrazolinone (111). The reaction proceeds through an azo (108) and a tetrazene (109) intermediate, followed by hydrolysis under the alkaline conditions of the reaction to the carbonyl compound (110). An unexplained oxidation leads to the 1,3-diaryl tetrazolinone (111) either directly or through the intermediate 110a (Scheme 15).18,35 A similar reaction occurs between a diazonium salt and the potassium salt of phenyl hydrazonomethane disulfonic acid (Scheme 15).175... 

The S-oxygenation of the hexaamine-dithiophenolate macrocycles should provide a potential entry into the novel class of binucleating polyamine-disulfonate and -disulfinate macrocycles. Indeed, such ligands can be prepared by the oxidation of dinuclear nickel complexes of the parent hexaaza-dithiopheno-late macrocycles followed by the decomposition of the oxidation products in acidic solution. The dinuclear nickel complexes [Nin2(L36)(L )]+ (L = Cr (70) and OAc (71)) of the hexaaza-diphenylsulfonate ligand (L36)2- (Fig. 38) are obtained by... 

Stretford A process for removing hydrogen sulfide and organic sulfur compounds from coal gas and general refinery streams by air oxidation to elementary sulfur, using a cyclic process involving an aqueous solution of a vanadium catalyst and anthraquinone disulfonic acid. Developed in the late 1950s by the North West Gas Board (later British Gas) and the Clayton Aniline Company, in Stretford, near Manchester. It is the principle process used today, with over 150 plants licensed in Western countries and at least 100 in China. 

Although most oxidations of sulfinic acids lead to sulfonic acids, some do not. Oxidation with Co(III) gives the corresponding a-disulfones in reasonably good yield (104) (Denzer et al., 1966). The mechanism of this synthetically useful reaction is not known. Two possibilities have been suggested (Denzer et... 

Absorption-oxidation processes oxidize absorbed H2S directly to elemental sulfur in solution (1). The principal example in current industrial use is the Stretford process (3). The chemistry of the process can be represented by the following idealized equations (ADA represents anthraquinone disulfonic acid) ... 

The use of six equivalents of dihydrogen peroxide leads to a clean conversion of the dithiolate complex to the disulfonate compound. Earlier studies on oxidation of nickel thiolates showed that oxidations with dioxygen stop at monosulfinates. Our observation and the characterization of the first chelating bis-sulfonato nickel complex formed from the direct oxidation of a mononuclear nickel dithiolate, may also provide new insight into the chemistry of sulfur-rich nickel-containing enzymes in the presence of oxygen. 

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