- Methods for preparation of disilathianes
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Several literature methods for preparation of disilathianes were reexamined and new procedures were developed. Two methods especially useful for the preparation of hexamethyldisilathiane were the reaction between lithium metal, sulfur, and TMS chloride in THF, and the reaction between Li2S and TMS chloride in THF at room temperature. These two procedures may also be used to prepare other hexaalkyldisilathianes. Other methods investigated for the preparation of hexamethyldisilathiane included (a) reaction between commercial anhydrous Na2S and TMS chloride in N,N'-dimethylpropyleneurea or HMPA, (b) production of a highly-reactive Na2S by reaction between sodium dispersion and sulfur, followed by reaction with TMS chloride in THF at room temperature, and (c) reaction between sulfur, NaH, and TMS chloride in N,N'-dimethylpropyleneurea.
- Curphey, Thomas J.
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- Convenient Syntheses of Hexamethyldisilathiane and Tetramethyldisilathiane
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Hexamethyldisilathiane and 1,1,3,3-tetramethyldisilathiane are prepared in excellent yields in a one-pot procedure by treating in situ generated disodium sulfide with chlorotrimethylsilane and chlorodimethylsilane, respectively.
- So, Jeung-Ho,Boudjouk, Philip
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- Dithiophosphorylation of nerol and geraniol trimethylsilyl derivatives
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Reaction of tetraphosphorus decasulfide with О-(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl)-trimethylsilanes affords О,О-bis(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl) S-(trimethylsilyl)dithiophosphates.
- Nizamov,Terenzhev,Nizamov,Shumatbaev,Batyeva,Cherkasov
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- Preparation method of hexamethyl disilicon sulfide
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The invention discloses a preparation method of hexamethyl disilicon sulfide, wherein the preparation method comprises the following preparation steps: (1) introducing inert gas into a 3000 mL four-mouth flask, adding bulk metal lithium and anhydrous tetrahydrofuran, and reacting; (2) adding sublimed sulfur powder in batches for reaction; (3) after the addition of the sulfur powder is completed, slowly dropwise adding 1270 mL of trimethylchlorosilane for reaction; and (4) after dropwise adding is finished, keeping the temperature at 35-50 DEG C, continuously reacting for 2-4 hours, raising the temperature, carrying out atmospheric distillation to remove a solvent, carrying out reduced pressure distillation to obtain a product with the purity of 90%, collecting the product, and further rectifying to obtain a qualified product with the purity of more than 98%. According to the technical scheme disclosed by the invention, the hexamethyl disilicon sulfide preparation method which is energy-saving, environment-friendly and simple and convenient to operate is realized.
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Paragraph 0005; 0026-0064
(2021/06/13)
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- Zinc Tin Chalcogenide Complexes and Their Evaluation as Molecular Precursors for Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe)
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A series of five heteronuclear zinc tin chalcogenide complexes with the general formula [(tmeda)Zn(SnR2)2E3] (1-R, E = S; R = Me, Ph, tBu; 2-R, E = Se; R = Ph, tBu) have been synthesized and characterized by X-ray crystal structure analysis. In all cases, the six-membered ZnSn2E3 rings exhibit twist boat conformation. The presence of the molecular structures in solution is confirmed by 119Sn and 77Se NMR spectroscopy. Cothermolysis experiments using a mixture of complexes 1-R or 2-R and [(iPr3PCu)2(EC2H4E)]2 as a copper source were monitored by thermogravimetry and temperature dependent X-ray powder diffraction to examine the thermolysis reaction. According to Rietveld refinement, the solid residue consists of Cu2ZnSnS4 (up to 78 wt %) or Cu2ZnSnSe4 (up to 43 wt %) as the main product, respectively.
- Fuhrmann, Daniel,Dietrich, Stefan,Krautscheid, Harald
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p. 13123 - 13131
(2017/11/15)
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- Facile Construction of Yttrium Pentasulfides from Yttrium Alkyl Precursors: Synthesis, Mechanism, and Reactivity
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Treatment of the yttrium dialkyl complex TpMe2Y(CH2Ph)2(THF) (TpMe2 = tri(3,5 dimethylpyrazolyl)borate, THF = tetrahydrofuran) with S8 in a 1:1 molar ratio in THF at room temperature afforded a yttrium pentasulfide TpMe2Y(κ4-S5) (THF) (1) in 93% yield. The yttrium monoalkyl complex TpMe2CpYCH2Ph(THF) reacted with S8 in a 1:0.5 molar ratio under the same conditions to give another yttrium pentasulfide [(TpMe2)2Y]+[Cp2Y(κ4-S5)]? (10) in low yield. Further investigations indicated that the S52- anion facilely turned into the corresponding thioethers or organic disulfides, and released the redundant S8, when it reacted with some electrophilic reagents. The mechanism for the formation of the S52- ligand has been investigated by the controlling of the reaction stoichiometric ratios and the stepwise reactions.
- Zhang, Fangjun,Zhang, Jie,Zhou, Xigeng
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p. 2070 - 2077
(2017/02/26)
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- Synthesis and crystal structures of [(iPr3P)2Cu(μ- ESiMe3)(InMe3)] (E = S, Se): Lewis acid-base adducts with chalcogen atoms in planar coordination
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The structures of [(iPr3P)2Cu(μ-SSiMe 3)(InMe3)] and [(iPr3P)2Cu(μ- SeSiMe3)(InMe3)] were determined by single-crystal X-ray diffraction. Both complexes are Lewis acid-base adducts of the InMe3 acceptor and the chalcogen donor atom linking a Me3Si group and a (iPr3P)2Cu moiety. They are very unstable under atmospheric conditions and decompose at ambient temperatures. Results of DFT calculations for these complexes and the related hypothetical [(Me 3P)2Cu(μ-SSiMe3)(InMe3)] compound show that the unusual planar coordination of the chalcogen atoms is due to steric crowding. Lewis acid-base adducts of trimethylindium and phosphane-stabilized copper(I) (trimethylsilyl)chalcogenolates were synthesized and characterized by X-ray crystal structure determination. They are very unstable under atmospheric conditions and decompose at ambient temperatures. DFT calculations reveal that the unusual planar coordination of the chalcogen atoms is due to steric crowding. Copyright
- Biedermann, Ralf,Kluge, Oliver,Fuhrmann, Daniel,Krautscheid, Harald
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p. 4727 - 4731
(2013/09/24)
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- Bis(oligosilanyl)chalcogenides [Me3Si)xMe3-xSi]2E, alkalimetal oligosilanylchalcogenolates (Me3Si)xMe3-xSi-EMI and oligosilanylchalcogenols (Me3Si)xMe3-xSi-EH (E = S, Se, Te) syntheses and NMR study
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Bis(oligosilanyl)chalcogenides [(Me3Si)x Me3-x Si]2E, alkalimetal oligosilanylchalcogenolates (Me3Si)x Me3-x Si-EMI and oligosilanylchalcogenols (Me3Si)x Me3-x Si-EH (x=1-3; E=S, Se, Te) were synthesized and characterized by 1H-, 13C-, 29Si-, 77Se- and 125Te-NMR spectroscopy. Trends of NMR parameters (chemical shifts, coupling constants) are discussed.
- Lange, Heike,Herzog, Uwe
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- Synthesis of organophosphorus compounds in terms of elemental phosphorus, sulfur and their derivatives
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We have developed new facile methods for synthesizing various organophosphorus compouds on the basis of elemental phosphorus and sulfur, phosphorus sulfides and esters of thiophosphorous acids.
- Batyeva, Elvira S.,Nizamov, Il'yas S.,Kursheva, Lidiya I.,Frolova, Liliya V.
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- New routes to heterocyclic selenium sulfides
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New synthetic routes for heterocyclic selenium sulfides are described and the identification of the molecular species by 77Se NMR spectroscopy is discussed. The reaction of [Ti(Me5C5)2S3] and Se2Cl2 produces initially a mixture of 1,2-Se2S6, 1,5-Se2S6 and 1,2,3,4,5-Se5S3 that can be inferred to be formed as a consequence of a rapid decomposition of 1,2-Se2S3. The product distribution is consistent with a series of selenium-atom transfer reactions as well as a dimerization of a four-atomic species that can be thought to be formed in the early stages of the reaction. The treatment of (Me3Si)2Se with Se2S5Cl2 produces initially 1,2,3-Se3S5 and the reaction of (Me3Si)2S and Se2S5Cl2 a mixture of 1,2-Se2S6, 1,5-Se2S6, and SeS7. These products imply that the reactant chloride is a mixture of Cl-Se-S5-Se-Cl and Cl-Se-Se-S4-S-Cl. Upon prolonged standing of all reaction mixtures described above, an equilibrium of several heterocyclic selenium sulfides is formed with the product distribution governed by the molar ratio of sulfur and selenium. The abundance of 77Sc chemical shift data has enabled the quantitative discussion on the trends and has facilitated a more reliable assignment of resonances to different molecular species. Acta Chemica Scandinavica 1998.
- Pekonen, Pentti,Taavitsainen, Jari,Laitinen, Risto S.
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p. 1188 - 1193
(2007/10/03)
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- DIALKYL TRIMETHYLSILYL TETRATHIOPHOSPHATES. SYNTHESIS AND TRANSFORMATIONS
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We have developed an efficient method for synthesizing dialkyl trimethylsilyl tetrathiophosphates, which react with aldehydes, acetals, ortho esters, thioacetals, bis(thiocyanato)methane, diethyl disulfide, and alkyl halides to give a number of new tetrathiophosphate derivatives.
- Nizamov, I.S.,Kuznetsov, V.A.,Batyeva, E.S.,Al'fonsov, V.A.
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p. 1196 - 1198
(2007/10/02)
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- CONVENIENT SYNTHESIS OF S-TRIMETHYLSILYL ESTERS OF DITHIO- AND TETRATHIOPHOSPHORIC ACIDS
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S-Trimethylsilyl esters of dithio- and tetrathiophosphoric acids were obtained in the reaction of tetraphosphorus decasulfide with alkoxy- and alkylthiotrimethylsilanes, trimethylsilyl enol ethers and bis(trimethylsilyloxy)alkylenes and phenylene. Key words: S-Trimethylsilyl esters of dithio- and tetrathiophosphoric acids; tetraphosphorus decasulfide; alkoxy- and alkylthiotrimethylsilanes; trimethylsilyl enol ethers; bis(trimethylsilyloxy)alkylenes
- Nizamov, Il'yas,Kuznetzov, Vladislav A.,Batyeva, Elvira S.,Al'Fonsov, Vladimir A.,Pudovik, Arkady N.
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p. 179 - 186
(2007/10/02)
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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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- NEUE DARSTELLUNG, SCHWEFELINSERTION UND HYDROLYSE DER PHENYL(TRIMETHYLSILYL)STIBANE
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Reaction of Mg and Me3SiCl with Ph2SbCl or PhSbCl2 gives Ph2SbSiMe3 (1) or PhSb(SiMe3)2 (2).Sulfur inserts into 1 to give Ph2SbSSiMe3 (3).Products of action of S8 on 2 are 3, PhSb(SSiMe3)2 (4), (Me3Si)2S, and Sb2S3.Hydrolysis or methanolysis of 1, or 2 give Ph2SbH (5), or PhSbH2 (6), respectively.Key words: Diphenyl(trimethylsilyl)stibane; phenylbis(trimethylsilyl)stibane; diphenyl(trimethylsilyl-thio)stibane; diphenylstibane; phenylstibane.
- Ates, M.,Breunig, H. J.,Guelec, S.
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p. 129 - 134
(2007/10/02)
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- Gas- Phase Ion Chemistry of Siloxide and Silamide Ions by Using the Flowing Afterglow. Unusual Rearrangements Involving SiO and SiS Bond Formation
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Siloxide ions undergo O/S exchange reactions with suitable sulfur-containing neutrals, e.g.H3SiO- + CS2 -> H3SiS- + COS.Silamide ions similarly undergo NR/O and NR/S exchange reactions together with nucleophilic displacement reactions, e.g.: .No simple correlation between rate and mechanism is observed for all the studied reactions.
- O'Hair, Richard A.J.,Sheldon, John C.,Bowie, John H.,Damrauer, Robert,DePuy, Charles H.
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p. 489 - 496
(2007/10/02)
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- BIS(TRIMETHYLSILYL)THIOKETONE
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Tris(trimethylsilyl)methylsulphenylbromide undergoes facile Me3SiBr elimination to give bis(trimethylsilyl)thioketone.
- Ricci, Alfredo,Degl'Innocenti, Alessandro,Fiorenza, Mariella,Dembech, Pasqualle,Ramadam, Nazmi,et al.
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p. 1091 - 1092
(2007/10/02)
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- SILYLATION DU THIOPHENE: UNE SYNTHESE ORIGINALE ET PRATIQUE DE L'HEXAMETHYLDISILYLTHIANE ET DE BUTENYLSILANES
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Complete silylation of thiophene by the Me3SiCl/Li/THF reagent affords the easily separated hexamethyldisilylthiane (80percent) and 1,1,4,4-tetrakis(trimethylsilyl)-2-butene (85percent).The latter leads to the unexpected 4,4-bis(trimethylsilyl)-1-butene (75percent) when treated with excess ICl.The reductive silylation in this case is a convenient method for desulphuration.
- Laguerre, Michel,Dunogues, Jacques,Duffaut, Norbert,Calas, Raymond
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p. C17 - C19
(2007/10/02)
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- Gas-phase Thermolyses. Part 3. Gas-phase Thermolysis of Silylated Thionocarboxylic Acid Derivatives: a Route to Thioketens?
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The unimolecular gas-phase thermolytic decomposition of three silylated thionocarboxylic acid derivatives (2b), (3), and (8) have been studied by the flash vacuum thermolysis-field ionization mass spectrometry technique in the temperature range from 783 to 1404 K in order to elucidate its possible applicability as a route to thioketens.Only very minor amounts of the expected thioketens were found, whereas the corresponding ketens were obtained as the major products.A possible mechanism for keten formation is discussed.
- Carlsen, Lars,Egsgaard, Helge,Schaumann, Ernst,Mrotzek, Herbert,Klein, Wolf-Ruediger
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p. 1557 - 1562
(2007/10/02)
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- SILICIUM-VERBINDUNGEN MIT STARKEN INTRAMOLEKULAREN STERISCHEN WECHSELWIRKUNGEN X. NEUE WEGE ZU 1,3,2,4-DITHIADISILETANEN
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2,2,4,4-Tetraorganyl-1,3,2,4-dithiadisiletanes containing bulky organyl groups are obtained by copyrolysis of the disilanes R3Si-SiR3 with sulfur or sulfur hexafluoride, or better by reaction of the disilanes R2HSi-SiHR2 (R=CH3, i-C3H7, cyclo-C6H11, t-C4H9) with sulfur.In the case of R=t-C4H9 a considerable amount of the t-butyl groups is isomerized to the less crowded isobutyl groups.Monomeric silathiones R2Si=S are not available by this route.The sulfur insertion reaction into 1,1-di-t-butyl-1-silacyclobutane yields 2,4-di-t-butyl-2,4-dipropyl-1,3,2,4-dithiadisiletane instead of the expected 1,1-di-t-butyl-1-sila-2-thiacyclopentane.The latter compound, however, results from the crown ether catalyzed cyclisation reaction of 3-bromopropyltrichlorosilane with Na2S followed by transalkylation with t-butyllithium.The iodosilanes R3SiI (R=i-C3H7, cyclo-C6H11) react with Na2S to give the corresponding hexaorganyldisilathianes in high yields.
- Weidenbruch, M.,Schaefer, A.,Rankers, R.
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p. 171 - 184
(2007/10/02)
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- The use of phosphorus pentafluoride as a fluorinating agent in organosilicon chemistry. III. Synthesis and characterization of some new fluorosiloxanes
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Although the silicon-oxygen bond of siloxanes and alkoxysilanes is readily cleaved by phosphorus pentafluoride, the silicon-hydrogen bond of hydrosiloxanes can be easily fluorinated at low temperatures by this reagent thus providing a convenient source of fluorosiloxanes. The synthesis and characterization of FSiH2OSiH3, (FSiH2)2O, F(CH3)HSiOSiH2CH3, and [F(CH3)HSi]2O are described.
- Kifer, Edward W.,Van Dyke, Charles H.
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p. 404 - 408
(2007/10/05)
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