Sodium sulfide reduction

The traditional treatment of nitrobenzene (1) with iron and acid, called Bechamp reduction, was employed almost exclusively in the production of aniline (2) and many aromatic amines until the 1960s1,2 (Scheme 1). The reduction is straightforward, and can also be achieved by catalytic hydrogenation, sodium sulfide reduction and zinc reduction with caustic soda. Nitrotoluenes and nitroxylenes are hydrogenated under pressure over a nickel catalyst supported on kieselguhr. The sulfide reduction is useful in selective reduction, such as of m-dinitrobenzene to m-nitroaniline. 

Thus reduction of the 5-thiocyanato group of 151 by zinc (333, 360, 361) or aqueous sodium sulfide (348. 362), hydrolysis of the thiouronium group (7, 363, 364), and deacetylation of the 5-acetylthiothiazole with cold piperidine (365) have been performed to yield the 5-mercapto-thiazole (Scheme 78). It must be pointed out that depending on the experimental conditions, bis(5-thiazolyl(sulfide may be observed as a byproduct (363, 365). Thus 5-amino-4-methylthiazole (152) treated with... 

Manufacture. The oldest method for producing Na2S is by the reduction of sodium sulfate with carbon in a refractory oven at 900—1000°C. Whereas this method is no longer used commercially in the United States, a variation is used to produce sodium sulfide captively during kraft pulp processing to replace lost sodium and sulfur values that were initiated into the system by merchant-suppHed sodium sulfide. In this method, sodium sulfate is added to the system in the recovery furnace, where it is reduced by carbon from the wood pulp to produce sodium sulfide. 

Chemical Properties. Anhydrous sodium sulfite is stable in dry air at ambient temperatures or at 100°C, but in moist air it undergoes rapid oxidation to sodium sulfate [7757-82-6]. On heating to 600°C, sodium sulfite disproportionates to sodium sulfate and sodium sulfide [1313-82-2]. Above 900°C, the decomposition products are sodium oxide and sulfur dioxide. At 600°C, it forms sodium sulfide upon reduction with carbon (332). 

Blends of polyester with cotton (qv) or viscose are first dyed with disperse dyes, then with sulfur dyes (see Fibers, polyester Fibers, regenerated CELLULOSics). Disperse and sulfur dyes can also be appHed simultaneously in a pad—dry—thermofix/chemical reduction pad—steam sequence. In this case, the sulfur dyes cannot be used in thein reduced form because of the effect of the sodium sulfide on the disperse dye. Therefore, this method is confined to the solubilized sulfur dyes or sulfur dyes in the dispersed form. 

This compound can be converted to l,5-diamino-4,8-dihydroxyanthraquiaone by reduction of nitro groups with sodium sulfide. 

Controlled reductions arc also possible with a variety of other reagents m-Trrfluoromethylnitrobenzene is converted to the azoxy derivative with hot potassium hydroxide-methanol [SS] but gives the arrune with hot sodium sulfide-sodium hydroxide solution [iS9] (equation 71)... 

Compounds 15 can be prepared either by acylation of bis(o-aminophenyl) ditelluride (88KGS276 89KGS120) or by reduction of A -acyl-2-trichlorotelluro-benzenes with sodium sulfide (88MI1). 

Dibenzo[d,g][l,5]telluroazocines 65 are the only representatives of Te, N-containing eight-membered heterocycles known thus far. Treatment of bis(2-bromomethylphenyl)tellurium dibromide 66 with methylamine followed by reduction of the reaction mixture with sodium sulfide gives, instead of the expected... 

Chlorins, e.g. 14, form adducts with osmium(VIII) oxide, which can be hydrolyzed in aqueous sodium sulfide to bacteriochlorindiols, e g. 2, or isobacteriochlorindiols, e.g. 3. Thus, similar to diimide reductions of chlorins, metal-free tetraphenylchlorin 14 (M = 2H) is selectively oxidized to a corresponding bacteriochlorin 2 whereas the zinc chlorin gives an isobac-teriochlorin 3 on oxidation with osmium(VIII) oxide.40 With less symmetrical chlorins, very complex mixtures of constitutional isomers and stereoisomers are formed by /i-bishydroxyla-tion.17... 

Similarly, reduction of zinc(II) 9,16,23-tri-(tm-butyl)-l-nitrophthalocyanine by sodium sulfide leads to the corresponding amino compound in 68% yield.319... 

This combustion process results in the reduction of inorganics, leading to a molten smelt of sodium carbonate (Na2C03) and sodium sulfide (NajS) on the furnace floor, which is discharged to a tank and dissolved to form green liquor. 

Sulfinic acids can be prepared by reduction of sulfonyl chlorides. Though mostly done on aromatic sulfonyl chlorides, the reaction has also been applied to alkyl compounds. Besides zinc, sodium sulfite, hydrazine, sodium sulfide, and other reducing agents have been used. For reduction of sulfonyl chlorides to thiols, see 19-57. 

Toxic pollutants found in the mercury cell wastewater stream include mercury and some heavy metals like chromium and others stated in Table 22.8, some of them are corrosion products of reactions between chlorine and the plant materials of construction. Virtually, most of these pollutants are generally removed by sulfide precipitation followed by settling or filtration. Prior to treatment, sodium hydrosulfide is used to precipitate mercury sulfide, which is removed through filtration process in the wastewater stream. The tail gas scrubber water is often recycled as brine make-up water. Reduction, adsorption on activated carbon, ion exchange, and some chemical treatments are some of the processes employed in the treatment of wastewater in this cell. Sodium salts such as sodium bisulfite, sodium hydrosulfite, sodium sulfide, and sodium borohydride are also employed in the treatment of the wastewater in this cell28 (Figure 22.5). 

Electrochemically generated nickel is very selective for the reduction of aromatic nitro compounds into anilines, in which alkenyl, alkynyl, halo, cyano, formyl, and benzyloxy groups are not affected.84 Sodium sulfide has been used for the selective reduction of aromatic nitro group in the presence of aliphatic nitro groups (Eq. 6.44).85... 

Tertiary nitro compounds are converted into the corresponding thiols by the reaction with sodium sulfide and sulfur (S8) in DMSO followed by the reduction with Al-Hg. (Eq. 7.12). Secondary and primary nitro compounds do not give thiols in these reactions instead, a complex set of product is formed.13... 

Alkaline delignification in the form of the Kraft or Sulfate process is now the most widely used method of lignin removal. It uses a mixture of sodium hydroxide and sodium sulfide—the latter being produced in the recovery process by the reduction of sodium sulfate... 

Selective reduction (e.g., partial reduction of one of two nitro groups) is carried out with an alkali sulfide, such as sodium hydrogen sulfide NaHS ( sodium sulfhy-drate ) or sodium sulfide Na2S, in an aqueous or alcoholic solution. Azo groups are not affected by this method. The reaction converts sodium hydrogen sulfide or sodium sulfide mainly to sodium thiosulfate. 

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