Sodium hydrogen sulfide, reaction with

Anhydrous gaseous or Hquid hydrogen sulfide is practically nonacidic, but aqueous solutions are weakly acid. The for the first hydrogen is 9.1 X 10 at 18°C for the second, is 1.2 x 10 . Reaction of hydrogen sulfide with one molar equivalent of sodium hydroxide gives sodium hydrosulfide with two molar equivalents of sodium hydroxide, sodium sulfide forms. Hydrogen sulfide reacts with sodium carbonate to produce sodium hydrosulfide... 

If tin and sulfur are heated, a vigorous reaction takes place with the formation of tin sulfides. At 100—400°C, hydrogen sulfide reacts with tin, forming stannous sulfide however, at ordinary temperatures no reaction occurs. Stannous sulfide also forms from the reaction of tin with an aqueous solution of sulfur dioxide. Molten tin reacts with phosphoms, forming a phosphide. Aqueous solutions of the hydroxides and carbonates of sodium and potassium, especially when warm, attack tin. Stannates are produced by the action of strong sodium hydroxide and potassium hydroxide solutions on tin. Oxidizing agents, eg, sodium or potassium nitrate or nitrite, are used to prevent the formation of stannites and to promote the reactions. 

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. 

The most effective synthesis for thietanones is the eliminative cyclization of halogenated ketones with hydrogen sulfide ions in the presence of bases (Eq. lOb). The reaction of 1,3-dibromoketone derivatives with sodium hydrogen sulfide produced 3-thietanones in association with a five-membered cyclic disulfide (Eq. 10c). 

Likewise, perfluoronaphthalene has been reacted with sodium hydrogen sulfide.42 The reaction was carried out with a 2 1 ratio of hydrogen sulfide to perfluoronaphthalene in the more polar dimethylformamide/ethylene glycol (5 1) solvent system at — 6 °C over 45 min, yielding... 

The preparation of highly functionalized cyclopentadiene derivatives may by achieved by using oxalenes or their pyrylium salts (90 and 92, respectively), (see Scheme 14, where X = O). In this way, azalenes 26,51 29,8Z 88 32,51 or 3651 can be obtained by heating salts (90) with primary amines in dimethyl-formamide (Eq. 6). The reaction with sodium hydrogen sulfide gives thialenes... 

This approach is illustrated by the reaction of several immonium salts, obtained by Vilsmeier reaction with sodium hydrogen sulfide (equation 47) to afford a series of stable enamino thioaldehydes306. 

When hydrogen sulfide reacts, with mercuric chloride in neutral or acid solution, or when mercury and sulfur are ground together, black mercuric sulfide is formed. Under certain conditions, this material can be converted into the red modification by the continued action of soluble alkali sulfides. The reaction of mercuric chloride and sodium thiosulfate gives the red form if the ratio of the concentrations is higher than 1 4d The red sulfide is also produced when the substance Hg(SH)NCS is boiled with concentrated ammonium thiocyanate solution or when hydrogen sulfide is conducted into a warm mercuric salt solution in the presence of acetic acid and an excess of ammonium thiocyanate, or thiourea.2,3... 

Reaction of the 2-amino-1,3-dithiolylium bromide (156) with sodium hydrogen sulfide in DMF/acetic acid at room temperature leads to a 91% yield of l,3-dithiole-2-thione (21) (75S277). 

Long reaction times lead to the disappearance of the blue color of thione 1, related to the addition of a second molecule of hydrogen sulfide to give colorless gem-dithiols 3. Aromatic derivatives (R = Ar) are less prone to further addition of hydrogen sulfide, whereas with aliphatic derivatives (R = alkyl), gem-dithiols are generally the final reaction products and can be isolated and fully characterized.18 gem-Dithiols 3 can be converted into thioacylsilanes 1 by neutralization of the thionation solution with solid sodium hydrogen carbonate. With this procedure, enolizable acylsilanes 2 (R = R CH2) are stereoselectively transformed into Z-a-silyl enethiols 4 (vide infra). 

Bacchetti et al. used the same method, and also the reaction with sodium hydrogen sulfide, to prepare 2-aroyl-l,3,4-thiadiazoline-5(4)-thiones (18). 

Bulk aluminum may undergo the following dangerous interactions exothermic reaction with butanol, methanol, 2-propanol, or other alcohols, sodium hydroxide to release explosive hydrogen gas. Reaction with diborane forms pyrophoric product. Ignition on contact with niobium oxide + sulfur. Explosive reaction with molten metal oxides, oxosalts (nitrates, sulfates), sulfides, and sodium carbonate. Reaction with arsenic trioxide + sodium arsenate + sodium hydroxide produces the toxic arsine gas. Violent reaction with chlorine trifluoride, Incandescent reaction with formic acid. Potentially violent alloy formation with palladium, platinum at mp of Al, 600°C. Vigorous dissolution reaction in... 

A powerful oxidizer. Explosive reaction with acetaldehyde, acetic acid + heat, acetic anhydride + heat, benzaldehyde, benzene, benzylthylaniUne, butyraldehyde, 1,3-dimethylhexahydropyrimidone, diethyl ether, ethylacetate, isopropylacetate, methyl dioxane, pelargonic acid, pentyl acetate, phosphoms + heat, propionaldehyde, and other organic materials or solvents. Forms a friction- and heat-sensitive explosive mixture with potassium hexacyanoferrate. Ignites on contact with alcohols, acetic anhydride + tetrahydronaphthalene, acetone, butanol, chromium(II) sulfide, cyclohexanol, dimethyl formamide, ethanol, ethylene glycol, methanol, 2-propanol, pyridine. Violent reaction with acetic anhydride + 3-methylphenol (above 75°C), acetylene, bromine pentafluoride, glycerol, hexamethylphosphoramide, peroxyformic acid, selenium, sodium amide. Incandescent reaction with alkali metals (e.g., sodium, potassium), ammonia, arsenic, butyric acid (above 100°C), chlorine trifluoride, hydrogen sulfide + heat, sodium + heat, and sulfur. Incompatible with N,N-dimethylformamide. 

Hydrogen sulfide also reacts by nucleophilic substitution with alkyl halides and alcohols under appropriate conditions to form thiols (Scheme 10) (see Chapter 4, p. 42). The reaction with an alkyl halide is generally facilitated by using sodium hydrogen sulfide (NaSH) rather than hydrogen sulfide since NaSH is a much better nucleophile. Hydrogen sulfide also adds to ketones to give gem-dithiols (13) (Scheme 11). 

Sodium hydrogen sulfide can be used for the preparation of thiols (19) by reaction with alkyl halides. A large excess of sodium hydrogen sulfide must be employed to avoid formation of the dialkyl sulfide (Scheme 17) (see Chapter 4, p. 41). 

In this connection it is perhaps worthwhile to reconsider the synthesis of benzothiazoline-2-thiones. These substances can, as already mentioned, be made from o-nitrochlorobenzene with sodium hydrogen sulfide and carbon disulfide (method C). Starting from 0- or w-halo anilines, benzothiazoline-2-thiones are also obtainable with carbon disulfide in strong alkali (55). The intermediate in this reaction is an aryne (CXXXIII). 

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