Dithionite oxidation

Carbomethoxyamino-2,l,4-benzothiadiazines, such as 192, can be made by the action of methyl isothiocyanatomethanoate on 2-nitroaniline, followed by reductive ring-closure with sodium dithionite. Oxidation with 3-chloroperbenzoic acid gives the corresponding 2-oxide 193 (71-... 

In the further scans, this first wave is not observed because in the aforementioned potential region, the electrode surface is no longer a pure platinum one but is a rearranged platinum hydroxide surface39. The results described in section 6.2 showed that the limiting-current plateau of the second oxidation wave (first scan) is controlled by transport of dithionite. This indicates that electron transfer from dithionite to PtOH and/or PtO is a much faster process than transport of dithionite towards the electrode. This is confirmed by the fact that in the further scans an identical limiting-current is obtained. The third oxidation wave in the first scan (second wave for the other scans) is attributed to the oxidation of sulphite described earlier. It is formed as a reaction product of the sodium dithionite oxidation and also of the homogeneous decomposition of sodium dithionite. Also in this case, a hysteresis effect is observed for the sulphite forward/back-ward sweep oxidation wave. 

Mechanism of the charge-transfer kinetics of dithionite oxidation... 

The condition of the platinum electrode surface can play an important role in the kinetics of electrochemical reactions, but for the kinetics of dithionite oxidation it was found that the platinum surface condition did not seriously interfere (see section 6.3). 

In the preceding sections, it was mentioned several times that the limiting-current of the first wave of the sodium dithionite oxidation is suitable for electroanalytical purposes because of the transport-controlled nature of this limiting-current. Indeed, it was proven earlier that this limiting-current can be correlated with the Levich equation (1.15), showing a linear relationship between limiting-current and sodium dithionite concentration. 

Calibration plot between peak current of the sodium dithionite oxidation reaction and its concentration at a bare gold electrode (curve 1) and at a CoTSPc-modified (curve 2) and CoTSPor-modified (curve 3) gold electrode. T=298.0K. 

The experimental design is simple. A given sample of nitrogenase equipped with an ATP-generating system, Mg2+, and reductant is allowed to turn over without substrate (case I), and the dihydrogen production is monitored. The amount of dihydrogen produced is found to be equal (within experimental error) to the dithionite oxidized (50). Therefore, the electron balance equation is ... 

Sodium dithionite, Na2S204, decreased the remission function at all wavelengths greater than 300 nm, but the largest decreases occurred in the visible region. Polcin and Rapson [93] attributed this to the reduction of simple quinones and coniferaldehyde. Kuys and Abbot [99] made similar observations in a spectroscopic study of dithionite bleaching of radiata pine TMR However, they suggested that coniferaldehyde was reduced by sodium bisulfite formed as a dithionite oxidation product, not by dithionite itself. 

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

Another method employed is the treatment of aqueous solutions of aminophenols with activated carbon (81,82). During this procedure, sodium sulfite, sodium dithionite, or disodium ethylenediaminotetraacetate (82) is added to increase the quaUty and stabiUty of the products and to chelate heavy-metal ions that would catalyze oxidation. Addition of sodium dithionite, hydrazine (82), or sodium hydrosulfite (83) also is recommended during precipitation or crystallization of aminophenols. 

With hot metals, sulfur dioxide usually forms both metal sulfides as well as metal oxides. In aqueous solution, sulfur dioxide is reduced by certain metals or by borohydrides to dithionites. 

Ana.lytica.1 Methods. Various analytical methods involve titration with oxidants, eg, hexacyanoferrate (ferricyanide), which oxidize dithionites to sulfite. lodimetric titration to sulfate in the presence of formaldehyde enables dithionite to be distinguished from sulfite because aldehyde adducts of sulfite are not oxidized by iodine. Reductive bleaching of dyes can be used to determine dithionite, the extent of reduction being deterrnined photometrically. Methods for determining mixtures of dithionite, sulfite, and thiosulfates have been reviewed (365). Analysis of dithionite particularly for thiosulfate, a frequent and undesirable impurity, can be done easily by Hquid chromatography (366). 

Sodium dithionite is considered only moderately toxic. The solution is reported to have an LD q (rat, oral) of about 5 g/kg. As with sulfites, fairly large doses of sodium dithionite can probably be tolerated because oxidation to sulfate occurs. However, irritation of the stomach by the Hberated sulfurous acid is expected. As a food additive, sodium dithionite is generally recognized as safe (GRAS) (367). 

Traditionally, these dyes are appHed from a dyebath containing sodium sulfide. However, development in dyeing techniques and manufacture has led to the use of sodium sulfhydrate, sodium polysulfide, sodium dithionite, thiourea dioxide, and glucose as reducing agents. In the reduced state, the dyes have affinity for cellulose (qv) and are subsequendy exhausted on the substrate with common salt or sodium sulfate and fixed by oxidation. 

Later, a completely different and more convenient synthesis of riboflavin and analogues was developed (34). It consists of the nitrosative cyclization of 6-(A/-D-ribityl-3,4-xyhdino)uracil (18), obtained from the condensation of A/-D-ribityl-3,4-xyhdine (11) and 6-chlorouracil (19), with excess sodium nitrite in acetic acid, or the cyclization of (18) with potassium nitrate in acetic in the presence of sulfuric acid, to give riboflavin-5-oxide (20) in high yield. Reduction with sodium dithionite gives (1). In another synthesis, 5-nitro-6-(A/-D-ribityl-3,4-xyhdino) uracil (21), prepared in situ from the condensation of 6-chloro-5-nitrouracil (22) with A/-D-ribityl-3,4-xyhdine (11), was hydrogenated over palladium on charcoal in acetic acid. The filtrate included 5-amino-6-(A/-D-ribityl-3,4-xyhdino)uracil (23) and was maintained at room temperature to precipitate (1) by autoxidation (35). These two pathways are suitable for the preparation of riboflavin analogues possessing several substituents (Fig. 4). 

Most vat dyes are based on the quinone stmcture and are solubilized by reduction with alkaline reducing agents such as sodium dithionite. Conversion back to the insoluble pigment is achieved by oxidation. The dyes are appHed by either exhaust or continuous dyeing techniques. In both cases the process is comprised of five stages preparation of the dispersion, reduction, dye exhaustion, oxidation, and soaping. 

Another approach uses the reaction of 6-chloro-5-nitropyrimidines with a-phenyl-substituted amidines followed by base-catalyzed cyclization to pteridine 5-oxides, which can be reduced further by sodium dithionite to the heteroaromatic analogues (equation 97) (79JOC1700). Acylation of 6-amino-5-nitropyrimidines with cyanoacetyl chloride yields 6-(2-cyanoacetamino)-5-nitropyrimidines (276), which can be cyclized by base to 5-hydroxypteridine-6,7-diones (27S) or 6-cyano-7-oxo-7,8-dihydropteridine 5-oxides (277), precursors of pteridine-6,7-diones (278 equation 98) (75CC819). 

Conversely, sulfites can act as oxidants in the presence of strong reducing agents e.g. sodium amalgam yields dithionite, and formates (in being oxidized to oxalates) yield thiosulfate ... 

SO2. Consistent with this, air-oxidation of alkaline dithionite solutions at 30-60° are of order one-half with respect to [8204 ]. Acid hydrolysis (second order with respect to [8204 ]) yields thiosulfate and hydrogen sulfite, whereas alkaline hydrolysis produces sulfite and sulfide ... 

Fig. 3. Cation-exchange chromatography of protein standards. Column poly(aspartic acid) Vydac (10 pm), 20 x 0.46 cm. Sample 25 pi containing 12.5 pg of ovalbumin and 25 pg each of the other proteins in the weak buffer. Flow rate 1 ml/min. Weak buffer 0.05 mol/1 potassium phosphate, pH 6.0. Strong buffer same +0.6 mol/1 sodium chloride Elution 80-min linear gradient, 0-100% strong buffer. Peaks a = ovalbumin, b = bacitracin, c = myoglobin, d = chymotrypsinogen A, e = cytochrom C (reduced), / = ribonuclease A, g = cytochrome C (oxidised), h = lysozyme. The cytochrome C peaks were identified by oxidation with potassium ferricyanide and reduction with sodium dithionite [47]...

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