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Physical Data: colorless gas; bp -60.75 °C; mp -85.60 °C; d (0 °C) 1.539 g L-1 (more dense than air); dipole moment (C6H6) 0.85-0.97 D. pKa1 (aq) 6.88, pKa2 (aq) 14.15; E0(H2S -> S + 2H+ + 2e-) -0.14 V.
Solubility: sol H2O (0.12 mol L-1 at 20.1 °C); sol polar and nonpolar organic solvents.
Form Supplied in: liquefied gas in steel cylinders.
Handling, Storage, and Precautions: extremely toxic, malodorous gas; use of a well-ventilated hood is a necessity; a scrubber flask containing 20% aqueous NaOH prevents loss of H2S to the atmosphere. The sense of smell is paralyzed at concentrations of 150-250 ppm and death may ensue at concentrations above 300 ppm. An irritant to the eyes and mucous membranes; highly flammable; ignites spontaneously in air at around 250 °C; mixtures of H2S (4.5-45%) and air are explosive; corrosive (especially in aqueous solutions) to many metals; anhydrous H2S is unreactive to stainless steel at ambient temperatures.
Formation of Na2S, NaSH, K2S, and KSH.
Passage of H2S into excess aq NaOH or KOH yields Sodium Sulfide, and K2S, which can be used in situ.6 Sodium Hydrogen Sulfide and Potassium Hydrogen Sulfide are produced in ethanolic base saturated with H2S;7 addition of, for example, excess KOEt yields K2S.7a In the formation of KSH, H2S is passed into an ethanolic KOH solution until the mixture does not test alkaline with phenolphthalein.7c Solutions of hydrogen sulfide salts are in equilibrium with the sulfide and H2S: 2NaSH &ibond; Na2S + H2S.
Thiols or their salts are obtained by displacement reactions2 by SH- or S2- (derived from H2S) on primary or secondary halides or sulfonate esters, on oxiranes and aziridines, on quaternary ammonium salts, and on activated aromatic halides (eq 1).8 The displacement of chloride ion shown in eq 1 takes precedence over the addition reaction of H2S to the nitrile group (see below). Halonitrobenzenes may undergo both substitution of halogen and reduction of the nitro group.2a,6,9 High temperatures are required for unactivated aryl halides (eq 2).10 Elimination and thioether formation are side reactions with aliphatic substrates. To minimize thioether formation, an excess of H2S is employed (see the above equilibrium).
Thiolacids and their derivatives are obtained from the acid chloride or anhydride (eqs 5 and 6).7c,12 Potassium thiotosylate, useful in the synthesis of thiotosylates, is obtained in a similar way from tosyl chloride (eq 7).13 The solution must be saturated with H2S. gem-Dithiols are obtained by treatment of ketones with H2S and an organic base (or the preformed enamine may be used) (eq 8),14 and best yields are obtained with cyclic ketones. Use of the ketimine or enamine gives satisfactory yields (53-83%) of gem-dithiols of acyclic ketones.14b Addition of H2S to propionaldehyde in the presence of Chlorotrimethylsilane results in the silyloxythiol (eq 9).15 A Michael-type of addition of H2S to a,b-unsaturated systems provides b-mercapto derivatives that are readily desulfurized, thus providing a method for the selective reduction of the carbon-carbon double bond (eq 10).16 Attempted reduction of this double bond (eq 10) by borohydride, hydride, and silane reagents was unsuccessful.
Derivatives of thiocarboxylic acids4c,24 are obtained from H2S and orthoesters (eq 15),25 carboxylic acid ester enolates (eq 16),26 and imino esters.27 A method for reduction of a tertiary alcohol to an alkane involves its conversion to a thioformate ester followed by treatment with Tri-n-butylstannane (eq 17).27b Addition of H2S to thioimino esters provides derivatives of dithiocarboxylic acids (eq 18).4d,28 The thioamide function4e,29 is obtained by addition of gaseous or liquid H2S to nitriles (eq 19),17b,30 ynamines,31 various imines (eq 20),32 and to orthoesters or chloroform in the presence of an amine (eq 21).32f,33 Thioureas, thiobiurets, and thio heterocycles,32d,34 thioimides (eq 22),32b,35 and thioacylhydrazines36 are obtained by similar reactions.
Hydrogen sulfide reduces nitro groups (eq 25),5,9,48 nitroso groups,49 azido groups,50 the S=O group (eq 26),51 the chlorosulfonyl group,52 sulfur-sulfur,53 sulfur-nitrogen,54 nitrogen-nitrogen,55 carbon-nitrogen,11b,56 and carbon-mercury57 bonds, the C-I and C-O bonds of some a-iodo and a-alkoxy ketones,58 osmate esters,59 and 1,2,3-tricarbonyl compounds60a and their hydrates60b-d (the 2-carbonyl functionality is reduced to the alcohol and dimers (eq 27)60d may be formed). Benzil is reduced quantitatively either to deoxybenzoin or benzoin, depending on conditions.14c The carbonyl group of aldehydes and ketones undergoes nucleophilic reduction with H2S and a reducing thiol to give good yields of thiols via thiocarbonyl derivatives (eq 28).61 The reduction of the azido group in 4-azidobutyryl derivatives of alcohols provides a mild method for deprotection of the hydroxy function (eq 29).50a Reduction of the azido group by elemental hydrogen instead of H2S in the deprotection scheme may be accompanied by the reduction of other functional groups (eg alkene).
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