- The reaction of (η-C5H5)2Ti(CO)2 with sulfoxides
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Sulfoxides are reduced by (η-C5H5)2Ti(CO)2 to give sulfides in high yield while sulfones and phosphine oxides do not react.
- Chen, T. L.,Shaver, Alan,Chan, T. H.
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Read Online
- Reactions of Dichloroethenes with Sulfur in the System Hydrazine Hydrate–KОН
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Vinylidene chloride and 1,2-dichloroethene react with sulfur in the system hydrazine hydrate–KОН with the formation of polyvinylenesulfide oligomer of molecular mass 1750–6120 Da containing also vinylenehydrazine and vinylenechloride links in the Z-configuration, and 1,4-dithiine in the yield up to 46%. In aqueous-hydrazine layer polysulfide anions Sn2– (n = 1–4), mainly S22– were found. The mechanism of formation of oligomers and 1,4-dithiine is suggested, which includes in the first stage dehydrochlorination of dichloroethenes and generation of chloroacetylene.
- Levanova,Nikonova,Grabel’nykh,Russavskaya,Albanov,Rozentsveig,Korchevin
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Read Online
- 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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Read Online
- A process for the preparation of isoflavones propanethiol
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The invention discloses a method for synthesizing isopropyl mercaptan from propylene and hydrogen sulfide. According to the method, a heat insulation type fixed bed reactor is used and isopropyl mercaptan is synthesized of hydrogen sulfide and propylene in the presence of a solid acid catalyst according to a continuous production process. The method disclosed by the invention has the advantages that the reaction conditions are easy to control, the yield is high, the process is simple, and the environmental pollution is reduced.
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Paragraph 0052; 0053
(2017/04/03)
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- Dithiooxamide as an Effective Sulfur Surrogate for Odorless High-Yielding Carbon-Sulfur Bond Formation in Wet PEG200 as an Eco-Friendly, Safe, and Recoverable Solvent
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In this study, we have employed dithiooxamide, a solid, odorless, and commercially available compound, as a sulfur surrogate for the preparation of dialkyl sulfides from available alkyl halides in high yields. This sulfur transfer agent was also used for a copper-catalyzed high-yielding preparation of diaryl sulfides from their available aryl halides and for the preparation of thia-Michael adducts in high yields. All the reactions were performed under odorless conditions in wet PEG200 (PEG = polyethylene glycol), which is an eco-friendly, safe, and recoverable solvent. The protocols were easily applicable to large-scale operation.
- Firouzabadi, Habib,Iranpoor, Nasser,Gorginpour, Forough,Samadi, Arash
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supporting information
p. 2914 - 2920
(2015/05/04)
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- Hydrogenation of sulfoxides to sulfides under mild conditions using ruthenium nanoparticle catalysts
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The first demonstration of the hydrogenation of sulfoxides under atmospheric H2 pressure is reported. The highly efficient reaction is facilitated by a heterogeneous Ru nanoparticle catalyst. The mild reaction conditions enable the selective hydrogenation of a wide range of functionalized sulfoxides to the corresponding sulfides. The high redox ability of RuO x nanoparticles plays a key role in the hydrogenation.
- Mitsudome, Takato,Takahashi, Yusuke,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information
p. 8348 - 8351
(2014/08/18)
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- Highly efficient deoxygenation of sulfoxides using hydroxyapatite-supported ruthenium nanoparticles
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We report the first example of the deoxygenation of sulfoxides using heterogeneous catalysts with alcohols as environmentally friendly reducing reagents. Hydroxyapatitesupported Ru nanoparticles (RuNPs/HAP) act as a highly efficient and reusable heterogeneous catalyst for deoxygenation of sulfoxides using alcohols as reductants. The catalytic activity of Ru nanoparticles is outstanding compared to other metal nanoparticles such as Pt, Pd, Rh, and Au nanoparticles. RuNPs/HAP can also catalyze the selective deoxygenation of various sulfoxides, giving the corresponding sulfides in excellent yields.
- Takahashi, Yusuke,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information
p. 420 - 422
(2014/04/17)
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- Cyanuric chloride as promoter for the oxidation of sulfides and deoxygenation of sulfoxides
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This Letter discusses the use of cyanuric chloride as an efficient promoter for the chemoselective oxidation of sulfides to the corresponding sulfones in the presence of H2O2 as the terminal oxidant. Sulfoxides were also found to undergo deoxygenation to sulfides with cyanuric chloride and potassium iodide system. The reaction is broad in scope and easy to perform.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Sohrabnezhad, Samira
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experimental part
p. 6420 - 6423
(2011/12/21)
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- Process and catalyst for synthesis of mercaptans and sulfides from alcohols
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A process and catalyst blend for selectively producing mercaptans and sulfides from alcohols. The alcohol is reacted with hydrogen sulfide, in the presence of a catalyst blend containing a hydrotreating catalyst and a dehydration catalyst to convert the alcohol to mercaptan or sulfide in one-pass. The alcohols can include primary and secondary alcohols. The mercaptan or sulfide having less than about 30% unreacted alcohol contained therein.
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Page/Page column 7-8
(2008/06/13)
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- New ways of synthesis of 1,2-dithiole-3-thione
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Two new synthetic approaches to 1,2-dithiole-3-thione are proposed. The title compound is formed by thermolysis of dipropyl polysulfides (n-Pr) 2Sx (x = 3-4) and thermal decomposition of polysulfide dendrimers under reduced pressure. The latter reaction may be recommended for utilization of organochlorine waste products in the manufacture of epichlorohydrin, which are used for the synthesis of dendrimers. 2004 MAIK "Nauka/Interperiodica".
- Korchevin,Russavskaya,Yakimova,Deryagina
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p. 1754 - 1756
(2007/10/03)
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- An immobilized homogeneous catalyst for efficient and selective hydrogenation of functionalized aldehydes, alkenes, and alkynes
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An immobilized cationic rhodium(I) catalyst bearing the diphosphine 1,1′-bis(diisopropylphosphino)-ferrocene (DiPFc, 1) allows efficient and chemoselective hydrogenation of a range of functionalized aldehydes, as well as alkenes and alkynes, under mild conditions. This heterogenized catalyst system is convenient to prepare, is stable to air and moisture over extended periods, and is readily recycled.
- Burk,Gerlach,Semmeril
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p. 8933 - 8939
(2007/10/03)
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- Deoxygenation of sulfoxides and selenoxides with nickel boride
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The deoxygenations of a variety of acyclic sulfoxides and selenoxides have been reported with nickel boride in THF at 0-5°C in nearly quantitative yields. The deoxygenations are proposed to proceed by an oxidative-addition and reductive-elimination mechanism.
- Khurana, Jitender M.,Ray, Abhijit,Singh, Sarika
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p. 3829 - 3832
(2007/10/03)
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- Tellurium(IV) chloride/sodium iodide mediated facile and mild reduction of sulphoxides to sulphides
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Tellurium(IV) chloride/sodium iodide reagent system reduces dialkyl, diaryl and alkylaryl sulphoxides to the corresponding sulphides in high yield in acetonitrile at room temperature.
- Khan, R H,Rastogi, R C
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p. 293 - 294
(2007/10/02)
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- Concepts of sterically hindered resonance and buttressing effect: Gas-phase acidities of methyl-substituted benzoic acids and basicities of their methyl esters
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Two classical terms "Steric Hindrance to Resonance" and "Buttressing Effect" are revisited on the basis of the gas-phase acidities of nine methyl-substituted benzole acids and of the gas-phase basicities of their methyl esters, measured using FT- ICR spectrometry. By combining these data with published heats of formation of the neutrals and by using the principle of isodesmic reactions, relative enthalpies of formation were evaluated separately for the acid molecules, their anions (deprotonated), and their protonated cations (substituted by the protonated forms of the corresponding methyl esters). Energies of all species were also calculated at the semiempirical level (AMI). Substituent effects on the gas-phase acidity are similar to those on the acidity in water. All the methyl groups have a stabilizing polar effect, and o-methyl groups have a destabilizing steric effect, both effects increasing from the deprotonated forms to the acid molecules and then to the protonated forms. Separation of the two effects was attempted, assuming equal polar effects in the ortho and para positions. The results are internally consistent: their detailed analysis is in favor of a primary steric effect rather than a steric inhibition of resonance. The latter must be relatively weaker and operating only in 2,6-dimethyl derivatives, which are certainly nonplanar. In the literature this concept has been used too broadly, even for compounds for which the nonplanar conformation has not been proven. The concept of buttressing effect has been confirmed for methyl-substituted benzoic acids, but it is formulated more generally and more exactly. According to the new definition, it can be observed even for nonadjacent substituants.
- Decouzon, Michèle,Ertl, Peter,Exner, Otto,Gal, Jean-Fran?ois,Maria, Pierre-Charles
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p. 12071 - 12078
(2007/10/02)
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- HIGH-TEMPERATURE ORGANIC SYNTHESIS XXXVIII. THERMAL SYNTHESIS OF 1,2-DITHIOLE-3-THIONES FROM POLYSULFIDES
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The main product from the thermolysis of dipropyl polysulfides (C3H7)2Sn (n = 3-4) at 350-400 deg C is 1,2-dithiole-3-thione, and it is formed with yields of up to 52 percent. 4-Methyl-1,2-dithiole-3-thione was obtained from diisobutyl polysulfides (iso-C4H9)2Sn under analogous conditions with a yield of 68 percent.
- Turchaninova, L. P.,Sukhomazova, E. N.,Korchevin, N. A.,Deryagina, E. N.,Voronkov, M. G.
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p. 435 - 437
(2007/10/02)
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- Radical Cations from One-electron Oxidation of Aliphatic Sulphoxides in Aqueous Solution. A Radical Chemical Study
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Sulphoxide radical cations, (R2SO)+., have been observed upon one-electron oxidation of simple aliphatic sulphoxides by strongly oxidizing radicals with redox potentials >/=+2 V, e.g.SO4-., (CH3I)+., (CH3IICH3)+, or Ti2+ in pulse-irradiated aqueous solutions.They exhibit optical absorptions in the u.v. with λmax depending on the substituent (e.g. 300, 320, and 330 nm for R=Me, Et, and Pr, respectively).Extinction coefficients are of the order of 103 mol-1dm-3cm-1.The sulphoxide radical cations exist only at low pH and are probably best formulated in terms of an adduct with one water molecule, (R2SOOH2)+.The pK values for the equilibrium (R2SOOH2)+R2SO(OH). + H+ have been estimated to be 5.6, 6.1, and 6.5, for R=Me, Et, and Pr, respectively, from yield measurements.The neutral R2SO(OH). is identical with the hydroxyl radical adduct to sulphoxides formed at any pH in the reaction of R2SO + .OH, and decays irreversibly into R. + RSO2- + H+.The sulphoxide radical cationsare very good oxidants.Absolute rate constants have been measured for their reactions with a variety of electron donors, namely, organic sulphides, dithia compounds, disulphides, Br-, I-, and SCN-.The optical and kinetic results are discussed in the light of the electronic properties of the radical species.
- Kishore, Kamal,Asmus, Klaus-Dieter
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p. 2079 - 2084
(2007/10/02)
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- Electronic and steric effects in the dissociative displacement of thioethers from mixed phenyl(thioether)platinum(II) complexes
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A series of compounds of the type cis-[PtPh2L2], where L encompasses a wide range of thioethers of different steric and electron-donating characteristics, have been prepared and characterized. Most of these monomeric compounds exist in solution in equilibrium with the sulfur-bridged dimer [Pt2Ph4(μ-L)2] and the free thioether. Addition of small amounts of ligand in solution allows the stabilization of the monomeric form. Kinetic studies of the displacement of the thioethers with 2,2′-bipyridine (bpy) to yield [PtPh2(bpy)] in CH2Cl2 at 298.16 K, carried out in the presence of sufficient excess of [L] and [bpy] to ensure pseudo-first-order conditions, showed that the reactions follow a bivariate nonlinear rate law kobsd = a[bpy]/(b[L] + [bpy]) + c[bpy], which has the same form as that of similar systems for which a dissociative mechanism has been proposed. The reactivity decreases linearly with increasing σ-donor ability of the leaving thioether, with bulky substituents on sulfur playing an accelerating role. The relative sensitivities of the dissociative and associative processes to the inductive effects of the leaving group are compared and related to the degree of lengthening and weakening of the bond with the metal produced by the trans-activating group.
- Alibrandi, Giuseppe,Minniti, Domenico,Scolaro, Luigi Monsù,Romeo, Raffaello
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p. 1939 - 1943
(2008/10/08)
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- Reactivity of Chalcogen Cluster Polycations
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The chalcogen polycations S8(AsF6)2, S19(HS2O7)2, and Se4(HS2O7)2 are powerful oxidants entering into electron transfer reactions with hydrocarbons, aromatic compounds, and halides.
- Rosan, A. M.
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p. 377 - 378
(2007/10/02)
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- EFFET PROMOTEUR DES PHOSPHITES ALIPHATIQUES DANS L'ADDITION PHOTO AMORCEE D'H2S SUR LE PROPYLENE EN SOLUTION. I - ETUDE ANALYTIQUE
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Aliphatic phosphites have a promotor effect in the radical addition in solution of H2S to propylene photoinitiated as well by direct H2S irradiation as by added benzophenone irradiation.For this last reaction, the phosphite used being (CH3O)3P, the solvent polarity has no effect on the reaction.When the solvent used is a poor hydrogen donnor in a radical reaction, such as benzene, there is an induction period in the case of the benzophenone photoinitiated reaction performed in the presence of a phosphite.It increases for a given aliphatic phosphite with the phosphite concentration and varies with the aliphatic phosphites structure.Light intensity has nearly no effect on the development of the last reaction.
- Brehon, Annick,Couture, Axel,Combier, Lablache A.
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p. 839 - 850
(2007/10/02)
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- Synthetic Methods and Reactions. 112. Synthetic Transformations with Trichloromethylsilane/Sodium Iodide Reagent
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A new, convenient, and inexpensive alternative to the in situ equivalent of iodotrimethylsilane was developed.A mixture of trichloromethylsilane/sodium iodide in dry acetonitrile is found to be a more selective reagent than chlorotrimethylsilane/sodium iodide for the cleavage of ethers, esters, and lactones.Ethers are cleaved regioselectively by this reagent.Cleavage of esters and lactones also occured more readily with the present system.Conversion of alcohols, particularly tertiary and benzylic alcohols, to corresponding iodides is achieved in very short times at ambient temperatures.Deoxygenation of sulfoxides to sulfides is found to be instantaneous.Reductive dehalogenation of alicyclic α-halo ketones to the corresponding ketones has also been studied.The reagent is also used for the deprotection of acetals to carbonyl compounds.
- Olah, George A.,Husain, Altaf,Singh, Brij P.,Mehrotra, Ashok K.
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p. 3667 - 3672
(2007/10/02)
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- Reduction of Sulphoxides to Sulphides by Chlorosulphonyl Isocyanate/Sodium Iodide
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Sulphoxides are reduced to the corresponding sulphides in good yields by chlorosulphonyl isocyanate in the presence of sodium iodide in acetonitrile.
- Keshavamurthy, K. S.,Vankar, Y. D.,Dhar, D. N.
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- Chemical Conversions using Sheet Silicates: Novel Intermolecular Eliminations of Hydrogen Sulphide from Thiols
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Aliphatic primary and secondary thiols react in the interlamellar layers of ion-exchanged montmorillonite catalysts to produce dialkyl sulphides via intermolecular elimination of hydrogen sulphide; similar processes result in the production of diphenyl sulphide from benzenethiol and poly(phenylenemethylene) from α-toluenethiol.
- Ballantine, James A.,Galvin, Robert P.,O'Neil, Robert M.,Purnell, Howard,Rayanakorn, Mongkon,Thomas, John M.
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p. 695 - 696
(2007/10/02)
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- Phosphorus Tri-iodide (PI3), a Powerful Deoxygenating Agent
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On reaction with PI3 sulphoxides, selenoxides, aldehyde oximes, and primary nitroalkanes are transformed to sulphides, selenides, and nitriles, respectively.
- Denis, Jean Noel,Krief, Alain
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p. 544 - 545
(2007/10/02)
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