- Understanding hydrogen sulfide storage: Probing conditions for sulfide release from hydrodisulfides
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Hydrogen sulfide (H2S) is an important biological signaling agent that exerts action on numerous (patho)physiological processes. Once generated, H2S can be oxidized to generate reductant-labile sulfane sulfur pools, which include hydrodisulfides/persulfides. Despite the importance of hydrodisulfides in H2S storage and signaling, little is known about the physical properties or chemical reactivity of these compounds. We report here the synthesis, isolation, and characterization (NMR, IR, Raman, HRMS, X-ray) of a small-molecule hydrodisulfide and highlight its reactivity with reductants, nucleophiles, electrophiles, acids, and bases. Our experimental results establish that hydrodisulfides release H2S upon reduction and that deprotonation results in disproportionation to the parent thiol and S0, thus providing a mechanism for transsulfuration in the sulfane sulfur pool.
- Bailey, T. Spencer,Zakharov, Lev N.,Pluth, Michael D.
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supporting information
p. 10573 - 10576
(2014/08/18)
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- Generation of reactive oxygen species by a persulfide (BnSSH)
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Hydropersulfides (RSxSH) have been implicated as important intermediates in the cell-killing action of the anticancer natural products leinamycin and varacin. It has been suggested that persulfides can mediate the conversion of molecular oxygen to reactive oxygen species (O2 .-, H2O2, and HO.). Here, experiments with synthetic benzyl hydrodisulfide (BnSSH) provide direct evidence that persulfides readily decompose to produce reactive oxygen species under physiologically relevant conditions.
- Chatterji, Tonika,Keerthi, Kripa,Gates, Kent S.
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p. 3921 - 3924
(2007/10/03)
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- Heteroorganic betaines 3. * Reactions of betaines containing the +P-C-Si-S- fragment
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The [Ph3P+-CMe2-SiMe2-SEt]Br- salt was prepared by the reaction of betaine Ph3P+-CMe2SiMeR-S- (1a: R = Me) with EtBr. Acetylation of betaine 1a or Et3P+-CHMeSiMe2-S- (2a) afforded 2,2,6-trimethyl-1,3-dioxa-2-silacyclohex-5-ene-4-thione Me2SiOC(=S)CH=C(Me)O or the [Et3P+-CHMeSiMe2Cl]Cl- salt depending on the reagent ratio. The reactions of betaines 1a,b (1b: R = Ph) or 2 with compounds (R3Sn)2X (X = O or NMe) can be used for the generation of silanones [RMeSi=O] and silaneimines [RMeSi=NMe] in solutions. The reactivity of betaines Ph3P+-CHR1SiMeR2-S- (R1 = H or Me and R2 = Me or Ph) is determined by the equilibrium between the zwitterionic and ylide Ph3P=CR1SiMeR2SH tautomers that exist in solutions.
- Borisova,Zemlyanskii,Shestakova,Khrustalev,Ustynyuk,Chernyshev
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p. 933 - 941
(2007/10/03)
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- Spectroelectrochemical study of the nucleophilic substitution of diacyl disulfides by 2-nitrophenyl thiolate ions in N,N-dimethylacetamide
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S-Aryl thiol esters RC(O)SAr and ArS2- ions are the end products resulting from the reactions between bis(2-nitrophenyl) disulfide Ar2S2 and thiocarboxylate ions RC(O)S- (R = Me, Ph) at 20°C. The apparent SNAr process in fact occurs in two steps as shown by UV-vis absorption spectrophotometry coupled with voltammetry: (i) formation of diacyl disulfides [RC(O)]2S2 and ArS- ions by redox exchange; (ii) subsequent nucleophilic substitution of 2-nitrophenyl thiolate ions at the carbonyl carbon of diacyl disulfides.
- Ahrika,Anouti,Robert,Paris
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p. 1867 - 1874
(2007/10/03)
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- Linking agents and methods
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Compounds containing carbohydrate moieties or carboxyl groups are linked to either compounds containing thiol moieties or electron-deficient moieties by the use of linking agents of the formula STR1 in which R1 is NH2 -- or NH2 --NH--; R2 is --NH--C(O)--, --C(O)--NH--, or --C(O)--; R3 is C1 -C10 alkylene, C5 -C7 cyclic alkylene, arylene, phenyl-substituted C1 -C10 alkylene, benzyl-substituted C1 -C10 alkylene, or amino-substituted C1 -C10 alkylene; R4 is H, acetyl, STR2 where R5 is C1 -C5 alkyl; m is zero or 1; and n ia zero or 1.
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- BIS(BROMOMAGNESIUM) SULFIDE - A REAGENT FOR THE SYNTHESIS OF DIORGANIC SULFIDES
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Bis(bromomagnesium) sulfide was obtained by the reaction of ethylmagnesium bromide with hydrogen sulfide. In reaction with electrophilic reagents in THF or diethyl ether it gives good yields of symmetrical sulfides with a high degree of purity.
- Nedugov, A. N.,Pavlova, N. N.
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p. 1103 - 1104
(2007/10/02)
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- Synthesis and Conformation of 4,4,5,5-Tetramethyl-1,2-dithiane Mono-S-oxide
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The synthesis of the title compound (6), an interesting subject for the study of anomeric and other conformational effects, was attained from ethyl isobutyrate in eight steps, with an overall yield of 11percent.The synthetic route described herein involved the crucial displacement of both neopentylic tosylate groups in 2,2,3,3-tetramethyl-1,4-butanediol ditosylate; while several standard procedures led to the formation of unexpected products, purified potassium thioacetate in hexamethylphosphoramide afforded the required dithioacetate derivative.The mechanistic implications of the well- and bad-behaved reactions are discussed.From the results of variable-temperature NMR experiments it is concluded that the axial conformer of 6 dominates the equilibrium to such an extent that no contribution of the equatorial isomer is recorded.This result sudggests a ΔG0 3.0 kcal/mol for the conformational equilibrium of the parent 1,2-dithiane mono-S-oxide.
- Juaristi, Eusebio,Cruz-Sanchez, J. Samuel
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p. 3334 - 3338
(2007/10/02)
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- Bis(tributyltin) Sulfide: An Effective and General Sulfur-Transfer Reagent
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Bis(tributyltin) sulfide acts efficiently to transfer the sulfur atom as S(2-) to a variety of halide substrates to afford the corresponding symmetrical sulfides in good overall yield.
- Harpp, David N.,Gingras, Marc,Aida, T.,Chan, T. H.
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p. 1122 - 1124
(2007/10/02)
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- The Preparation and Some Reactions of Unsymmetrical Acyl Thioacyl Sulfides
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A number of unsymmetrical acyl thioacyl sulfides have been prepared and characterized by the reaction of piperidinium or sodium dithiocarboxylates with acyl chlorides or by desulfurization reaction of acyl thioacyl disulfides with triphenylphosphine.They are deep blue oils or light green crystals and very unstable thermally and for moisture.The n --> ?* transitions of the thiocarbonyl group of 1 appear in higher wave length region than those of the corresponding symmetrical bis(thioacyl) sulfides .Some reactions with nucleophiles are discussed.It was found that the symmetricallization reaction of these unsymmetrical acyl thioacyl sulfides occurs in the presence of base such as lithium ethanethiolate to give the symmetrical bis(thioacyl) disulfides in fair yield.
- Kato, Shinzi,Sugino, Katsumi,Matsuzawa, Yukihiko,Katada, Tomonori,Noda, Ippei,et al.
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p. 1798 - 1811
(2007/10/02)
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