Dithion

Although the synthesis of thiazolidine-2,4-dithione has been reported (357), no examples of a A-2-thiazoline-4-thione bearing a nonprotomeric group at C-2 are known. Some fused compounds are reported in Table 41. 

HIO3 iodic acid H2S2S4 dithionic acid... 

HNO4 peroxonitric acid H2S2O4 dithionous acid... 

Heavy water, see Hydrogen[ H] oxide Heazlewoodite, see rn-Nickel disulfide Hematite, see Iron(III) oxide Hermannite, see Manganese silicate Hessite, see Silver telluride Hieratite, see Potassium hexafluorosilicate Hydroazoic acid, see Hydrogen azide Hydrophilite, see Calcium chloride Hydrosulfite, see Sodium dithionate(III)... 

Sulfuric acid, H2SO4, the most important commercial sulfur compound (see Sulfuric acid and sulfur trioxide), and peroxymonosulfuric acid [7722-86-3] (Caro s acid), H2SO, are discussed elsewhere (see Peroxides and peroxide compounds, inorganic). The lower valent sulfur acids are not stable species at ordinary temperatures. Dithionous acid [15959-26-9] H2S2O4, sulfoxyHc acid [20196-46-7] H2SO2, and thiosulfuric acid [13686-28-7] H2S2O2 are unstable species. A discussion of efforts to isolate and characterize the unstable sulfur acids is given (330). 

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). 

Sodium hydrosulfite or sodium dithionate, Na2S204, under alkaline conditions are powerful reducing agents the oxidation potential is +1.12 V. The reduction of -phenylazobenzenesulfonic acid with sodium hydrosulfite in alkaline solutions is first order with respect to -phenylazobenzenesulfonate ion concentration and one-half order with respect to dithionate ion concentration (135). The SO 2 radical ion is a reaction intermediate for the reduction mechanisms. The reaction equation for this reduction is... 

Diene moieties, reactive in [2 + 4] additions, can be formed from benzazetines by ring opening to azaxylylenes (Section 5.09.4.2.3). 3,4-Bis(trifluoromethyl)-l,2-dithietene is in equilibrium with hexafluorobutane-2,3-dithione, which adds alkenes to form 2,3-bis-(trifluoromethyl)-l,4-dithiins (Scheme 17 Section 5.15.2.4.6). Systems with more than two conjugated double bonds can react by [6ir + 2ir] processes, which in azepines can compete with the [47t + 27t] reaction (Scheme 18 Section 5.16.3.8.1). Oxepins prefer to react as 47t components, through their oxanorcaradiene isomer, in which the 47r-system is nearly planar (Section 5.17.2.2.5). Thiepins behave similarly (Section 5.17.2.4.4). Nonaromatic heteronins also react in orbital symmetry-controlled [4 + 2] and [8 + 2] cycloadditions (Scheme 19 Section 5.20.3.2.2). 

Imidazole-4,5-dicarboxylic acids, coupling, 5, 403 decarboxylation, 5, 434 1-substituted synthesis, 5, 468 synthesis, 5, 362, 402, 484 Imidazole-4,5-dione, l-alkyl-2-phenyl-synthesis, 5, 129, 479 Imidazole-2,4-diones tautomerism, 5, 370 Imidazole-4,5-diones tautomerism, 5, 370 Imidazole-2,4-dithione, 5,5-diphenyl-tautomerism, 5, 370 Imidazole-2,4-dithiones tautomerism, 5, 370 Imidazolepropanol synthesis, 5, 486 Imidazoles accelerators epoxy resins, 1, 407... 

Indolo[2,3-d][l,3]thiazine-2,4-dithione formation, 4, 299 Indolothiazines synthesis, 4, 519 Indoloyl azides Curtius rearrangement, 4, 288 Indolyl anions acylation, 4, 232 alkylation, 4, 235 Michael-type additions, 4, 236 Indomethacin... 

Lumazine-6,7-dithione, 1,3-dimethyl-synthesis, 3, 292 Lumazines acylation, 3, 290... 

---