Sodium sulfide nonahydrate, reaction with

Reaction of Diorgano Tellurium Dihalides with Sodium Sulfide General Procedure A 15-fold molar excess of sodium sulfide nonahydrate is mixed with the diorgano tellurium di halide and the mixture is heated at 90-95° on a boiling water bath. When the mixture has become liquid, it is stirred for an additional 10 min. and then cooled. Water is added to dissolve the sulfide and the mixture is filtered to collect the solid diorgano tellurium product. Liquid diorgano tellurium products are extracted into petroleum ether. Products are purified by recrystallization or distillation. 

The reduction of alkyl tellurium tri halides is a convenient method for the preparation of the corresponding dialkyl ditellurium when the trihalides can be obtained by reactions other than the halogenolysis of the dialkyl ditellurium. Addition of tellurium tetrachloride to olefins and condensation with ketones produces alkyl tellurium trichlorides. Sodium sulfide nonahydrate" and sodium or potassium disulfite were used as reducing agents. 

The treatment of 3-phenyl- and 3-ferrocenyl-3-chloropropenal with sodium sulfide nonahydrate gave rise to intermediate 3-phenyl- and 3-ferrocenyl-3-thiopropenal, which produced with aniline the 1-phenyl- (29a) and l-ferrocenyl-3-phenylaminothioprope-non 29h. The reaction of 29a,h with iodine in methanol yielded the oxidized bis(2,5-diphenylisothiazolium) octaiodide 30a (85%) and 2-phenyl-5-ferrocenylisothiazolium pentaiodide 30h (91%) (99ZAAC511). The structures of these iodides 30a (X = 17 ) and 30h were confirmed by X-ray diffraction (99ZAAC511, Scheme 8). 30a (I8 ) also formed a layer structure with isothiazolium cations and polyiodide anions. 

Preparation of the lower dialkyl sulfides by the following general procedure has been described by McAllan and his co-workers 286 Sodium sulfide nonahydrate (1.5 moles) is dissolved in water (250 ml) in a three-necked flask fitted with a reflux condenser, dropping funnel, and stirrer, then the alkyl halide (2 moles) is added slowly with vigorous stirring. When the very exothermic reaction ceases, the mixture is heated under reflux for a further 3 h and the sulfide is distilled over in steam, separated, washed with water, 10% sodium hydroxide solution, and again water, dried over calcium chloride, and distilled. In this way were obtained dimethyl (b.p. 37.3°), diethyl (b.p. 92°),287 diisopropyl (b.p. 119.8°), dipropyl (b.p. 142.8°),288 and bis-(2-cyanovinyl) sulfide (m.p. 142-143°, from ethyl acetate-cyclohexane).289... 

Bis-(2,4-dinitrophenyl) sulfide 292 1-Chloro-l,4-dinitrobenzene (100 g) is dissolved in ethanol (11), and a melt of sodium sulfide nonahydrate (65.5 g) and sulfur (9 g) is added in small portions. A violent reaction occurs, which is completed by 3 hours boiling on a sand-bath. After cooling, the product is filtered off and washed, first, with ethanol and then with warm water to remove the sodium chloride. The product (86 g) has m.p. 280° (dec.). 

Diethyl sulfide 445 Sodium sulfide nonahydrate (120 g) in water (120 ml) is heated to the boiling point in a distillation flask (750-ml capacity) fitted to a very efficient descending condenser leading to a receiver that is cooled in ice. To this is added diethyl sulfate (155 g) at such a rate that the lively reaction proceeds without external heating. The distillate is saturated with sodium chloride, and the sulfide is separated in a separatory funnel, dried over calcium chloride, and distilled it has b.p. 90-92°, the yield being 78% (35 g). 

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