Sodium ethanedithiolate

CARBOXYL GROUPS Hydrazine hydrate. Sodium ethanedithiolate. Sodium trithio-carbonate. 

AHylestrenol (37) is prepared from (32), an intermediate in the synthesis of norethindrone. Treatment of (32) with ethanedithiol and catalytic boron trifluoride provides a thioketal. Reduction with sodium in Hquid ammonia results in the desired reductive elimination of the thioketal along with reduction of the 17-keto group. Oxidation of this alcohol with chromic acid in acetone followed by addition of aHyl magnesium bromide, completes the synthesis... 

BF3 Et20, EtSH, 25°, 40 min, 80-90% yield. Addition of sodium sulfate prevents hydrolysis of a dithioacetal group present in the compound replacement of ethanethiol with ethanedithiol prevents cleavage of a dithiolane group. 

At about the same time Pedersen s work was underway, Bradshaw and his coworkers had undertaken the systematic preparation of numerous mono- and polysulfur macrocycles The syntheses were carried out in a fashion similar to that shown in Eq. (6.3). The two principal sources of sulfur in the first paper from this groupwere sodium sulfide and 1,2-ethanedithiol. The latter was utilized in the presence of sodium hydroxide base. Ethanol was generally used as solvent and the reactions were conducted at high dilution. Products were purified either by vacuum distillation or recrystallization as appropriate. The yields were generally in the 5—30% range. 

Androst-4-ene-3,l7-dione 3-Ethylene Thioketal A solution of androst-4-ene-3,17-dione (1.42 g, 5 mmoles) in acetic acid (20 ml) is treated with ethanedithiol (0.47 g, 5 mmoles) and a solution of 0.45 of p-toluenesulfonic acid monohydrate in acetic acid (5 ml). After 1 hr at room temperature, the pale yellow solution is poured into water and the resulting suspension is extracted with chloroform. The chloroform solution is washed with water, 5 % sodium hydroxide solution and water, dried (Na2S04) and evaporated. Chromatography of the resulting oil (1.93 g) over silica gel yields androst-4-ene-3,17-dione bisethylene thioketal, mp 173-175° [0.16 g, eluted with petroleum ether-benzene (1 2)] and androst-4-ene-3,17-dione 3-ethylene thioketal, mp 173-176° [1.38 g (76%), eluted with benzene-ethyl acetate (19 1)]. 

Dithiocanes are represented by several compounds. The simultaneous slow addition of ethanedithiol and 1,4-dibromobutane to sodium ethoxide in ethanol gives 1,4-dithiocane (378 b.p. 47-48 °C/3 mmHg) in lowyield (78JA6416). Oxidation with NOBF4 gives, presumably via the dication (379), the monosulfoxide (380) in good yield. 

Ethanedithiol has been prepared from ethylene dichloride or ethylene dibromide and alcoholic potassium hydrosulfide from ethylene dibromide and alcoholic sodium hydrosulfide from ethylene dichloride or ethylene dibromide and alcoholic sodium hydrosulfide under pressure from ethylene dibromide and thiourea and by the catalytic hydrogenation with cobalt trisulfide or nickel-on-kieselguhr of the mixture resulting from the reaction of ethylene and sulfur. The present method is a modification of one described by Mathias. ... 

Trithianes are rare but routes established for the 3-methyl derivative (226) could provide the basis of more general methods. These include the chlorination of diethyl disulfide and the reaction of the sulfenyl chloride (227) with 1,2-ethanedithiol (74MI22601). 1,2,4,5-Tetrathiane (228) has been prepared by the cyclization of two equivalents of the bis sulfenyl chloride CH2Y2 (229 Y = SCI) or the bis Bunte salt CH2Y2 (230 Y = SSQ3Na) using sodium... 

Hydrogenolysis of the C-S bond can be achieved both by dissolving metal systems (sodium in liquid ammonia) or by catalytic methods, particularly with a finely divided reactive form of nickel known as Raney nickel. When the latter is combined with dithioacetal formation, using either ethanedithiol or propane-1,3-dithiol, the result is a mild method for reducing a carbonyl group to a methylene group. 

The two procedures are applicable to condensations of ketones with both ethanedithiol and -mercaptoethanol. Previous methods (see ref 3 for literature) include use of zinc chloride and sodium sulfate, hydrogen chloride in ether, p-toluenesulfonic acid in benzene with azeotropic distillation, and an exchange method. 

Reaction of 1,2-ethanedithiol with dichloromethyl methylether in the presence of sodium results in the formation of the 2-methoxy-l,3-dithiolane (360) (Scheme 65) <72HCA75>, whereas its reaction with phosgene yielded the l,3-dithiolan-2-one (361) <41RTC453>. 

To a suspension of diethoxyphenylbismuthine, prepared from dibromophenylbismuthine (4.46 g, 10 mmol) and sodium ethoxide (20 mmol) in absolute ethanol, was added dropwise at —30 to -40°C a solution of 1,2-ethanedithiol (10 mmol) in the same solvent. The temperature was gradually raised to 0°C and the resulting yellow precipitate was filtered and dried under vacuum. The crude product was purified by recrystallization from 1,2-ethanedithiol (3.13 g, 83%) [76ZAAC(423)47]. 

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