Reducing agents dithionites

Although we show the structure of dithionous acid in Table 15.8, only its salts are known and these are powerful reducing agents. Dithionite is prepared by reduction of sulfite in aqueous solution (equation 15.93) by Zn or Na amalgam and possesses eclipsed structure 15.48. 

Common reducing agents are hydrogen in the presence of metallic or complex catalysts (e.g. Ni, Pd, Pt, Ru, Rh), hydrides (e.g. alanes, boranes, LIAIH, NaBHJ, reducing metals (e.g. Li, Na, Mg, Ca, Zn), and low-valent compounds of nitrogen (e.g. NjHj, NjHJ, phosphorus (e.g. triethyl phosphite, triphenyiphosphine), and sulfur (e.g. HO-CHj-SOjNa = SFS, sodium dithionite = Na S O. ... 

Reaction of free-base porphyrin compounds with iton(II) salts in an appropriate solvent results in loss of the two N—H protons and insertion of iron into the tetradentate porphyrin dianion ligand. Five-coordinate iton(III) porphyrin complexes (hemins), which usually have the anion of the iton(II) salt for the fifth or axial ligand, ate isolated if the reaction is carried out in the presence of air. Iron(II) porphyrin complexes (hemes) can be isolated if the reaction and workup is conducted under rigorously anaerobic conditions. Typically, however, iton(II) complexes are obtained from iton(III) porphyrin complexes by reduction with dithionite, thiolate, borohydtide, chromous ion, or other reducing agents. 

Sodium dithionite is most stable and effective as a reducing agent in alkaline solutions, although with excess strong alkaH the following reaction... 

Dithionite is a stronger reducing agent than sulfite. Many metal ions, eg, Cu", Ag", Pb ", Sb ", and Bi ", are reduced to the metal, whereas TiO " is reduced to (346). Dithionite readily reduces iodine, peroxides, ferric salts, and oxygen. Some of the decolorizing appHcations of dithionite, eg, in clay bleaching, are based on the reduction of ferric iron. 

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. 

Prereduced Powders. These are usually made from press cake paste to which a reducing agent has been added, such as sodium sulfide, sodium hydrosulfide, or sodium dithionite, which solubili2e the dye in water. Before drying, the dye paste may be mixed with dispersing and stahi1i2ing agents to aid appHcation. 

For reductive bleaching of wool the two most popular chemicals are stabilized sodium dithionite (sodium hydrosulfite. Cl Reducing Agent 1) and thiourea dioxide (Cl Reducing agent 11). Most reductive bleaching of wool is carried out using stabilized dithionite (2—5 g/L) at pH 5.5—6 and 45—65°C for 1 h. Thiourea dioxide is more expensive than sodium dithionite, but is an effective bleach when appHed at the rate of 1—3 g/L at 80°C at pH 7 for an hour. 

Zinc hydrosulfite (zinc dithionite) is a powerhil reducing agent used in bleaching paper and textiles it is prepared from zinc dust and sulfur dioxide ... 

The reducing agents generally used in bleaching include sulfur dioxide, sulfurous acid, bisulfites, sulfites, hydrosulfites (dithionites), sodium sulfoxylate formaldehyde, and sodium borohydride. These materials are used mainly in pulp and textile bleaching (see Sulfur compounds Boron compounds). 

Dithionites. Although the free-dithionous acid, H2S2O4, has never been isolated, the salts of the acid, in particular zinc [7779-86-4] and sodium dithionite [7775-14-6] have been prepared and are widely used as industrial reducing agents. The dithionite salts can be prepared by the reaction of sodium formate with sodium hydroxide and sulfur dioxide or by the reduction of sulfites, bisulfites, and sulfur dioxide with metallic substances such as zinc, iron, or zinc or sodium amalgams, or by electrolytic reduction (147). 

Wool may also be bleached with reducing agents, usually after bleaching with hydrogen peroxide. This is the normal practice with wool blends. In the reducing step, 0.2—0.5% sodium dithionite solutions are often used at pH 5.5—7 for 1—2 h at 45—65°C. Faster bleaching is obtained with 2inc hydroxymethane-sulfinate [24887-06-7] below pH 3 and above 80°C. 

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. 

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 ... 

The parent acid has no independent existence and has not been detected in aqueous solution either. Sodium dithionite is widely used as an industrial reducing agent and can be prepared by reduction of sulfite using Zn dust, Na/Hg or electrolytically, e.g. ... 

Dithionites are strong reducing agents and will reduce dissolved O2, H2O2,12,103 and Mn04. ... 

The requirement for reduction prior to DNA alkylation and crosslinking was first demonstrated by Iyer and Szybalski in 1964 [29], and can be induced both by chemical reducing agents such as sodium dithionite and thiols in vitro and by various reductive enzymes such as DT-diaphorase (NAD(P)H-quinone oxidoreduc-tase) in vitro and in vivo [47]. Much work to characterize the mechanism of reductive activation and alkylation has been carried out, principally by the Tomasz and Kohn groups, and Figure 11.1 illustrates a generally accepted pathway for mitomycin C [16, 48-50] based on these experiments, which is very similar to the mechanism originally proposed by Iyer and Szybalski [29]. 

Cultivation of strictly anaerobic organisms requires not only that the medium be oxygen-free, but also that the redox potential of the medium be compatible with that required by the organisms. This may be accomplished by addition of reducing agents such as sulfide, dithionite, titanium(III) citrate, or titanium(IIl) nitrilotriacetate. Any of these may, however, be toxic so that only low concentrations should be employed. Attention has been drawn to the fact that titanium(III) citrate-reduced medium may be inhibitory to bacteria during initial isolation (Wachenheim and Hespell 1984). 

It is well known that quinizarin (22) is alkylaminated in air to give a mixture of l-alkylamino-4-hydroxyanthraquinone (23), l,4-bis(alkylamino)-anthraquinone (24), and 2-alkylaminoquinizarin (25) (Scheme 7). The reaction conditions affect the ratio of these products. In a nitrogen atmosphere, or in the presence of sodium dithionite as reducing agent, the main amination product is 24. The solvent effects of the reaction of leuco... 

This is by far the most important reaction of tetrazolium salts and accounts for the bulk of their many applications. A large variety of reagents can reduce tetrazolium salts, e.g., 53 to formazans, e.g., 51. Ascorbic acid, hydrazine, and hydroxylamine have been recommended for the preparation of formazans from tetrazolium salts.245 Stronger reducing agents such as ammonium sulfide, sodium amalgam, sodium dithionite, and catalytic hydrogenation can further reduce the formazans to the amidrazones, e.g.,... 

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