- Hypervalent iodine in synthesis. VI. The electrophilic arylation of diaryliodonium salts to sodium telluride
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Diaryliodonium salts readily take place electrophilic arylation at Te to afford symmetrical diaryl tellurides in good yields.
- You,Chen
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- Sodium telluride in N-methyl-2-pyrrolidone: An efficient telluration system for the synthesis of aromatic tellurides and ditellurides
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Sodium telluride prepared in situ from tellurium and sodium hydride in N-methyl-2-pyrrolidone was found to act as an efficient tellurating agent for nonactivated aromatic iodides, providing a simple route to a variety of diaryl tellurides, alkyl aryl tellurides and diaryl ditellurides.
- Suzuki,Nakamura
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- Co2(CO)8-mediated and -catalyzed carbonylation of diaryl diselenides and ditellurides to seleno and telluro esters
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Diaryl diselenides and ditellurides react with CO (5-100 atm) at 100-200 deg C in the presence of Co2(CO)8 to give the corresponding seleno and telluro esters in 21-96percent yield.The carbonylation proceeds catalytically in Co2(CO)8 in the presence of triphenylphosphine.It was shown unambiguously that benzoylcobalt tetracarbonyl, which is one of possible intermediates, reacts with diphenyl diselenide or ditelluride to give phenyl selenobenzoate or tellurobenzoate, respectively.
- Takahashi, Hidetaka,Ohe, Kouichi,Uemura, Sakae,Sugita, Nobuyuki
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- Phase transfer catalysis in synthesis of organylthio(organyltelluro) acetylenes
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Phase transfer reaction of diorganyl ditellurides with organyl-2,2-dichlorovinyl sulfides, using as phase transfer catalysts benzyltriethylammonium chloride or 18-crown-6 ether, was used as a new general method to prepare organylthio(organyltelluro)acetylenes R-S-C≡C-Te-R′. The organyltellurolate anion formed in the presence of NaOH is the reaction intermediate.
- Martynov, Alexander V.,Mirskova, Anna N.,Le Guillanton, Georges
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- Reaction of arylhydrazines with diaryl ditellurides in the air: Insight into bimolecular homolytic substitution on tellurium via Aryl–Te bond cleavage
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The reactivity of diaryl ditelluride and diaryl telluride toward aryl radicals was studied in detail. Diphenyl ditelluride underwent a bimolecular homolytic substitution (SH2) reaction with a phenyl radical generated from phenylhydrazine in the air, to afford diphenyl telluride in excellent yield. Based on this diphenyl telluride synthesis, a one-pot synthesis of unsymmetrical diaryl tellurides was developed by the SH2 reaction of in situ generated diphenyl telluride with arylhydrazines in the air. The selectivity of mono-/di-substitution and the reactivity of arylhydrazines depend on the nature of the substituents on the arylhydrazines, that is, electron-donating or -withdrawing group.
- Yamamoto, Yuki,Sato, Fumiya,Kodama, Shintaro,Nomoto, Akihiro,Ogawa, Akiya
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- Catalyst free one-pot synthesis of symmetrical diaryl tellurides with Te0/KOH
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A highly efficient new protocol for C-Te bond formation leading to symmetrical diaryl tellurides has been developed. The synthesis employed aryl iodides and elemental tellurium as starting materials in the presence of KOH. It is a one-pot reaction without using any catalyst. Utilizing this new protocol, a variety of aryl and heteroaryl iodides are reacted with elemental tellurium to afford the corresponding diaryl tellurides in good to excellent yields.
- Zhang, Shaozhong,Karra, Kranthi,Koe, Adam,Jin, Jin
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- Moessbauer studies of after effects of Auger ionization following internal conversion in organo-(129m)tellurium compounds
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The after effects of Auger ionization in diphenyl-telluride, dibenzyl telluride, and their dispersions in a solvent at 4.2 K, were compared with the same systems labeled with tellurium in the ground state, viz. 129Te.The Moessbauer emission, in the former case is preceded by Auger event and β decay, while in the latter case, it is preceded only by β decay.Three species were observed in the two compounds, I-, C6H5I or C6H5CH2I, and the third one has tentatively been identified as (C6H5)2I+ or (C6H5CH2)2I+.The formation of I- represents rupture of both bonds, i.e., complete fragmentation of the molecule.The probability of fragmentation was estimated with the help of matrix isolation experiments, as the electronically excited tellurium-129 ion formed by fragmentation of the molecule, following the Auger ionization, may interact with a neighboring organo-tellurium molecule in neat compounds, and enter combination.In about 85percent of the events in case of diphenyl telluride and 55percent in case of dibenzyl telluride, molecules escape complete fragmentation despite the fact that about 100 eV excitation energy may be deposited during charge neutralization.A novel mode for rapid disposal of energy is discussed.
- Nath, Amar,Sauer, Ch.,Halpern, A.
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- Chalcogen-Bonding Catalysis with Telluronium Cations
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Chalcogen bonding results from non-covalent interactions occurring between electrodeficient chalcogen atoms and Lewis bases. Among the chalcogens, tellurium is the strongest Lewis acid, but Te-based compounds are scarcely used as organocatalysts. For the first time, telluronium cations demonstrated impressive catalytic properties at low loadings in three benchmark reactions: the Friedel–Crafts bromination of anisole, the bromolactonization of ω-unsaturated carboxylic acids and the aza-Diels–Alder between Danishefsky's diene and imines. The ability of telluronium cations to interact with a Lewis base through chalcogen bonding was demonstrated on the basis of multi-nuclear (17O, 31P, and 125Te) NMR analysis and DFT calculations.
- Aubert, Emmanuel,Mamane, Victor,Pale, Patrick,Weiss, Robin
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supporting information
p. 19281 - 19286
(2021/07/25)
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- Late to the Party: Synthesis and Characterization of Tellurium and Selenium Half-Sandwich Complexes
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We report the synthesis and characterization of the first series of tellurium and selenium complexes featuring an ν5-cyclopentadienyl ligand. Reaction of Ph3TeX (X = Cl, S2CNEt2) with MCpR (M = Li, K; R = H, Me4, Me5) results in high yields of [Cp][TePh3] (1), [CpMe4][TePh3] (2), and [Cp*][TePh3] (3), respectively. Similarly, reaction of Ph3SeCl with LiCp and KCp? furnishes [Cp][SePh3] (4) and [Cp*][SePh3] (5). Each was characterized by X-ray crystallography, revealing similar ν5-coordination with little distortion from an idealized half-sandwich geometry, presumably from the remaining lone pair on tellurium and selenium. The Te-centroid distances are relatively long (1: 2.770(3), 2: 2.746(1), and 3: 2.733(1) ?), suggesting a mostly ionic interaction. Se-centroid distances (4: 2.748(3), 5: 2.707(2), 2.730(2) ?) were found to be surprisingly similar despite its smaller atomic radius. Compounds 2, 3, and 5 display rapid decomposition at room temperature, extruding a phenylated cyclopentadiene and the respective diphenylchalcogenide. The nature of bonding within these complexes was investigated through DFT methods and found to be primarily ionic in nature.
- Bart, Suzanne C.,Jones, Leighton O.,Kieser, Jerod M.,Schatz, George C.,Uible, Madeleine C.,Zeller, Matthias
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supporting information
p. 4104 - 4109
(2021/12/17)
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- Trichloroisocyanuric Acid-Promoted Synthesis of Arylselenides and Aryltellurides from Diorganyl Dichalcogenides and Arylboronic Acids at Ambient Temperature
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A transition-metal-free method for the synthesis of arylselenides and aryltellurides has been established based on the oxidative cross-coupling between diorganyl dichalcogenides and aryl boronic acids. With trichloroisocyanuric acid as an oxidant, the reaction proceeded smoothly to afford the desired products in 45–97% yields at ambient temperature. Three reaction reagents used in this method are stoichiometric and the oxidation by-product isocyanuric acid can be easily isolated and recovered. Besides of arylboronic acids, aryl trifluoroborates and aryl trihydroxyborates salts are also able to perform this transformation. (Figure presented.).
- Sun, Nan,Zheng, Kai,Sun, Pengyuan,Chen, Yang,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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p. 3577 - 3584
(2021/06/15)
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- Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
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An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.
- Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
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p. 2707 - 2712
(2020/03/11)
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- New routes for the synthesis of unsymmetrical diarylselenides: Effect of heat, light and ultrasound
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Herein, we report the photochemical coupling of diphenyldiselenides with substituted phenylhydrazine hydrochloride without catalyst. The protocol was developed not only in presence of sunlight and UV light but also under thermal condition for comparison study. Moreover, ultrasound assisted new catalytic protocol was developed using Ni(II)/L-proline system in DMSO with the advantage of shorter reaction time compared to earlier reports. We have also developed a new C-Se cross coupling reaction where phenylselenyl chloride and arylhydrazine hydrochlorides were effectively coupled using developed catalytic system.
- Sahani, Amber J.,Burange, Anand S.,Thakur, Seema D.,Jayaram, Radha V.
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- C-Te Cross-Coupling of Diaryl Ditellurides with Arylboronic Acids by Using Copper(I) Thiophene-2-carboxylate under Mild Conditions
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We describe the successful cross-coupling of diaryl ditellurides with arylboronic acids by using copper(I) thiophene-2-carboxylate (CuTC) under mild conditions. Although other studies have reported that highly polar solvents (such as DMSO) or bases are required, this reaction was completed by using CuTC and common solvents under neutral conditions at room temperature. This cross-coupling reaction was performed with diaryl ditellurides and arylboronic acids bearing various groups, affording the corresponding diaryl tellurides in good to excellent yields.
- Koguchi, Shinichi,Shibuya, Yuga,Igarashi, Yusuke,Takemura, Haruka
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supporting information
p. 99 - 103
(2019/01/04)
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- C-Se cross-coupling of arylboronic acids and diphenyldiselenides over non precious transition metal (Fe, Cu and Ni) complexes
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Various tetradentate and tridentate ligands such as salophane, bishydrazone, bisbenzimidazolyl pyridine and isonicotinohydrazide have been prepared. Transition metal complexes of these ligands with Cu, Ni and Fe have been further synthesized and characterized by UV–vis, IR, NMR and CHN analysis. Catalytic activity of the metal complexes was tested for the cross coupling of diarylchalcogenide with arylboronic acid in DMSO as solvent in presence of a base. These non-precious metal complexes catalysed cross coupling reactions smoothly in shorter reaction time compared to earlier reports with comparable yields.
- Sahani, Amber J.,Jayaram, Radha V.,Burange, Anand S.
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- Synthesis of symmetrical and unsymmetrical tellurides via silver catalysis
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We describe here a simple and efficient methodology for the cross-coupling reaction of diaryl ditellurides with aryl boronic acids catalyzed by AgNO3. The general applicability and wide substrate scope make this an interesting method for the synthesis of a series of symmetrical and unsymmetrical diaryl tellurides. This silver-catalyzed protocol tolerates a variety of diaryl ditellurides as well as aryl boronic acids by using only 10 mol% of AgNO3 to provide the desired products in high yields. The reaction mechanism was proposed after high resolution mass spectrometry analysis and the active (PhTe)2AgIII intermediate could be detected.
- Goldani, Bruna,do Sacramento, Manoela,Lenard?o, Eder J.,Schumacher, Ricardo F.,Barcellos, Thiago,Alves, Diego
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supporting information
p. 15603 - 15609
(2018/10/04)
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- Iron(0) nanoparticles mediated direct conversion of aryl/heteroaryl amines to chalcogenides via in situ diazotization
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A simple procedure for the synthesis of organo-chalcogenides has been developed by the reaction of aryl/heteroaryl amines with di-aryl/heteroaryl dichalcogenides in the presence of tBuONO and Fe(0) nanoparticles. The reaction proceeds via in situ diazotization followed by chalcogenation. A series of functionalized diaryl/aryl heteroaryl/diheteroaryl/aryl-alkyl selenides, sulfides and tellurides have been obtained by this procedure. Significantly, using this procedure 2,4-dinitroaniline is converted to (2,4-dinitrophenyl)(phenyl)selane which is known as thioredoxin reductase (TR) and glutathione reductase (GR) inhibitor. The reaction goes by a radical pathway and a plausible mechanism has been suggested.
- Panja, Subir,Maity, Pintu,Kundu, Debasish,Ranu, Brindaban C.
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supporting information
p. 3441 - 3445
(2017/08/10)
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- Carbon-carbon bond forming reactions via Pd-catalyzed detellurative homocoupling of diorganyl tellurides
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A simple and highly efficient method for the constructions of Csp-Csp, Csp2-Csp2 and Csp3-Csp3 bonds is reported. The symmetrical diaryl tellurides undergo detellurative homocouplings to afford symmetrical biaryl products. The reactions are carried out at ambient temperature using PdCl2 as a catalyst in the presence of Ag2O and Na2CO3. Similarly, the detellurative homocouplings of dibenzyl telluride and bis(phenylethynyl)telluride give bibenzyl and the conjugated diyne, respectively.
- Zhang, Shaozhong,Kolluru, Lalitha,Vedula, Souseelya K.,Whippie, Drew,Jin, Jin
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supporting information
p. 3594 - 3597
(2017/08/23)
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- Diarylation of chalcogen elements using arylboronic acids via copper- or palladium-catalyzed oxidative coupling
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Transition metal-catalyzed diarylations of sulfur, selenium and tellurium were achieved using arylboronic acids in air. A copper-catalyzed reaction of sulfur or selenium efficiently yielded numerous symmetrical diaryl sulfides or selenides in the presence of NH4BF4. However, the diarylation of tellurium was not possible using this method, and required a palladium catalyst in the presence of KI and air for the reaction to proceed.
- Taniguchi, Nobukazu
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p. 5818 - 5823
(2016/08/30)
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- Role of anagostic interactions in cycloplatination of telluroethers: Synthesis and structural characterization
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Abstract Reactions of K2PtCl4 with TeRRE′ gave complexes of composition [PtCl2(TeRRE′)2] (R/RE′ = Ph2(1a), o-tol2 (1b), Mes2(1c), Ph/Mes (1d), o-tol/Mes (1e)). The complex [PtCl2(TeMes2)2] in refluxing THF afforded a mononuclear cyclometalated complex [PtCl{(CH2C6H2Me2-4,6)TeMes}(TeMes2)] (2). It tends to remain in equilibrium with a binuclear derivative [Pt(μ-Cl){(CH2C6H2Me2-4,6)TeMes}]2 (3) in CDCl3 solution. The complexes 1d and 1e did not undergo cyclometalation reaction under similar reaction conditions. The 2 on treatment with PPh3 gave [PtCl{(CH2C6H2Me2-4,6)TeMes}(PPh3)] (4). All the complexes have been characterized by elemental analysis and NMR (1H, 31P, 125Te, 195Pt) spectroscopy. Anagostic interactions have been recognised for facilitation of cyclometalation reactions. The molecular structures of trans-[PtCl2(TeMes2)2] (1c), trans-[PtCl2(PhTeMes)2] (1d), trans-[PtCl2(o-tolTeMes)2] (1e), [PtCl{(CH2C6H2Me2-4,6)TeMes}(TeMes2)] (2) and [PtCl{(CH2C6H2Me2-4,6)TeMes}(PPh3)] (4) have been established unambiguously by single crystal X-ray diffraction analyses.
- Kolay, Siddhartha,Kumar, Mukesh,Wadawale, Amey,Das, Dasarathi,Jain, Vimal K.
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- Platinum-Mediated Activation of Coordinated Organonitriles by Telluroethers in Tetrahydrofuran: Isolation, Structural Characterization, and Density Functional Theory Analysis of Intermediate Complexes
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The reactions of [PtCl2(NCR)2] with telluroethers (ArAr′Te) in organic solvents have been investigated. The reactions in dichloromethane yield [PtCl2(TeArAr′)2], while those in tetrahydrofuran (THF) give different products depending on the steric demands of the aryl groups on tellurium, the molarity of the reactants, and the reaction conditions. The reactions between [PtCl2(PhCN)2] and TeArAr′ in 1:1 molar ratio at room temperature in THF yield several products, like [PtCl2(TeArAr′)2] (Ar/Ar′ = Ph/Ph, o-tol/Mes, Mes/Mes), [PtCl2(PhCN){NC(O)Ph[TeMes(o-tol)]}], and [PtCl2{NC(O)Ph(TeMes2)}2]. The reaction with TeMes2 in refluxing THF gave [PtCl2{NC(Ph)C4H7O}{NC(O)Ph(TeMes2)}] and [PtCl(TeMes2){Te(Mes)CH2C6H2Me2}], depending on the duration of heating. Reaction of [PtCl2(PhCN)2] with TeArMes afforded [PtCl2(TeArMes)2] (Ar = Ph, o-tol, and Mes), the formation of which decreased with increasing steric demand of the Ar group, together with [PtCl2{NC(O)Ph(TeArMes)}2]. The telluroether in the latter binds to nitrogen, and tellurium exists in the formal oxidation state of +4 (from XPS). The tellurium in these complexes exhibits secondary interactions with platinum (J(195Pt-125Te) = 309-347 Hz) and with the carbonyl oxygen. These complexes slowly dissociate in solution to give [PtCl2(TeMesAr){NC(O)Ph(TeMesAr)}], finally leading to the formation of [PtCl2(TeMesAr)2]. Molecular structures of trans-[PtCl2(PhCN){NC(O)Ph[TeMes(o-tol)]}], trans-[PtCl2{NC(O)Ph(TeMes2)}2], trans-[PtCl2{NC(Ph)C4H7O}{NC(O)Ph(TeMes2)}], trans-[PtCl2{NC(O)Ph[TeMes(o-tol)]}2], trans-[PtCl2(TeMes2){NC(O)Ph(TeMes2)}], trans-[PtCl2{NC(O)Me(TeMes2)}2], and [PtCl(Te-o-tol){NC(O)Ph}2] have been unambiguously established by single-crystal X-ray diffraction analyses. Density functional theory calculations for some of the complexes were performed, and geometrical parameters are in good agreement with the values obtained from X-ray analyses.
- Kolay, Siddhartha,Wadawale, Amey,Nigam, Sandeep,Kumar, Mukesh,Majumder, Chiranjib,Das, Dasarathi,Jain, Vimal K.
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p. 11741 - 11750
(2015/12/31)
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- An alternative approach to differentially substituted 2-oxazoline chalcogen derivatives
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In this study we present an alternative method to obtain several substituted mono or bis-2-oxazolines containing a chalcogen atom as a tether element. Alkylation of 2-tosyloximethylene-2-oxazoline with an appropriate sodium, lithium or potassium alkoxide yielded the corresponding ether. Introduction of sulfur or selenium was easily accomplished using the corresponding sodium salts. The 77Se NMR for alkyl or aryl 2-methylene-2-oxazoline selenides shows good correlation with the electronegativity pattern of substituents. Most products containing oxazolinyl-chalcogen were stable under the usual experimental conditions. However, the tellurium derivatives showed unusual sensitivity to light and oxygen, decomposing through a very complex mechanistic pathway. As a result of this oxidative process, 4,4-dimethyl-2-oxazoline-2-carbaldehyde could be isolated and fully characterized for the first time, in 17% yield.
- De Mello, Murilo B.M.,Clososki, Giuliano C.,Piovan, Leandro,De Oliveira, Alfredo R.M.
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- Solvent selective phenyl selenylation and phenyl tellurylation of aryl boronic acids catalyzed by Cu(II) grafted functionalized polystyrene
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A solvent-selective methodology for the phenyl selenylation and phenyl tellurylation of aryl boronic acids has been developed for the first time using a polymer supported Cu(II) catalyst. The catalyst was synthesized by anchoring Cu(OAc)2 onto a functionalized polystyrene with pyridine thiosemicarbazone ligand. It was then characterized properly by SEM, EDAX, FT-IR, TGA, and EPR experiments. The catalyst smoothly catalyzes phenyl selenylation of aryl boronic acids in water and phenyl tellurylation of aryl boronic acids in PEG-600, selectively. Thus a wide variety of unsymmetrical organodiaryl or aryl-heteroaryl selenides and tellurides have been synthesized by this protocol. The catalyst was recycled up to six runs without any appreciable loss of catalytic activity.
- Roy, Susmita,Chatterjee, Tanmay,Islam, Sk. Manirul
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supporting information
p. 779 - 783
(2015/01/30)
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- Cyclopalladation of telluro ether ligands: Synthesis, reactivity and structural characterization
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Treatment of [PdCl2(PhCN)2] with diaryl telluride in 1:2 molar ratio gave mononuclear palladium complexes, trans-[PdCl2(TeR2)2] (1) (R = Mes (1a) (Mes = 2,4,6-trimethylphenyl), Ph (1b), o-tol (1c) (o-tol = ortho-tolyl)). Reaction of [PdCl2(TeMes2)2] with one equivalent of [PdCl2(PhCN)2] or Na2PdCl4 with TeRR′ afforded chloro-bridged binuclear complexes, [Pd2(μ-Cl)2Cl2(TeRR′)2] (2) (R/R′ = Mes/Mes (2a); Mes/Ph (2b); Ph/Ph (2c)). A toluene-methanol solution of trans-[PdCl2(TeMes2)2] on refluxing for 30 minutes yielded a binuclear cyclopalladated complex, [Pd2(μ-Cl)2{CH2C6H2(4,6-Me2)TeMes)}2] (3). When the refluxing was prolonged, a mononuclear complex cis-[PdCl2{MesTeCH2C6H2(4,6-Me2)TeMes}] (4) was isolated. Treatment of palladium acetate with TeMes2 afforded an acetato-bridged analogue of 3, [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)TeMes}2] (5a) together with a very minor component, a tetranuclear complex, [Pd(μ-OAc)(μ-TeMes)]4 (6). This reaction with unsymmetrical tellurides, MesTeR, also gave cyclopalladated complexes [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)TeR}2] (R = o-tol (5b) and Ph (5c)) in which 2-methyl of the mesityl group of the telluride was exclusively metallated. The complex trans-[PdCl2(TeMes2)2] on refluxing in xylene gave palladium telluride, Pd7Te3. These complexes were characterized by elemental analyses, IR and NMR (1H, 13C and 125Te) spectroscopy. The molecular structures of trans-[PdCl2(TeMes2)2] (1a), [Pd2(μ-Cl)2Cl2(TeMes2)2]·2acetone (2a·2acetone), cis-[PdCl2{MesTeCH2C6H2(4,6-Me2)TeMes}] (4), [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)TeMes)}2]·toluene (5a·toluene), [Pd2(μ-OAc)2{CH2C6H2(4,6-Me2)Tetol-o}2] (5b) and [Pd(μ-OAc)(μ-TeMes)]4 (6) were established by single crystal X-ray diffraction analyses. The mononuclear complex 1a was isolated in two polymorphic forms each with the trans configuration. This journal is
- Kolay, Siddhartha,Kumar, Mukesh,Wadawale, Amey,Das, Dasarathi,Jain, Vimal K.
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p. 16056 - 16065
(2015/01/09)
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- Ultrasound-assisted, transition-metal-free synthesis of diaryl tellurides from aryl boronic acids: A possible free-radical mechanism
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The first rapid, catalyst-free synthesis of diphenyl tellurides from readily available diphenyl ditelluride and aryl boronic acids is reported. The high efficiency, general applicability and wide substrate scope, including heterocycles and other functional groups, make this method superior. The technique, which utilizes dimethyl sulfoxide solvent and ultrasound promotion, opens the door for the synthesis of diphenyl tellurides at 100 °C in air within a short time in high yields. Georg Thieme Verlag Stuttgart New York.
- Mohan, Balaji,Hwang, Sori,Jang, Seongwan,Park, Kang Hyun
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p. 2078 - 2082
(2014/10/15)
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- A convenient and efficient copper-catalyzed synthesis of unsymmetrical and symmetrical diaryl chalcogenides from arylboronic acids in ethanol at room temperature
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A simple and convenient approach for the synthesis of unsymmetrical diaryl chalcogenides (Te, Se, and S) has been developed by copper-catalyzed cross-coupling reaction of organoboronic acid with diaryl dichalcogenide in ethanol using NaBH4 in air or oxygen. The present methodology is highly practical for the synthesis of unsymmetrical diaryl tellurides with various functionalities such as -NO2, -F, -Br, and -COOH that have been obtained in good to excellent yields. Methodology is also effective for the synthesis of unsymmetrical diaryl selenides and sulfides. Moreover, symmetrical diaryl selenides have also been obtained from arylboronic acids using elemental selenium powder under optimized reaction conditions. The use of NaBH 4 is the key for the development of milder reaction conditions, which enable the construction of unsymmetrical diaryl chalcogenides from boronic acid substrates in ethanol at room temperature.
- Kumar, Amit,Kumar, Sangit
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p. 1763 - 1772
(2014/03/21)
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- Copper-catalyzed chalcogenation of aryl iodides via reduction of chalcogen elements by aluminum or magnesium
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Aluminum-induced copper-catalyzed coupling of aryl iodides with selenium or sulfur element could afford the corresponding diaryl selenides or sulfides in good yields. When magnesium chloride as an additive was employed, diaryl monoselenides and monosulfides were selectively obtained. On the contrary, the use of sodium carbonate produced diaryl diselenides and disulfides. The preparation of diaryl diselenides was necessary for magnesium as a reductant. Regrettably, tellurium was very low reactivity.
- Taniguchi, Nobukazu
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p. 10510 - 10515,6
(2012/12/12)
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- Negishi cross-coupling of organotellurium compounds: Synthesis of biaryls, aryl-, and diaryl acetylenes
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A functional group tolerant palladium-catalyzed Negishi coupling of diaryl tellurides with organozinc has been developed. This methodology permits efficient preparation of biaryls, aryl acetylenes and diaryl acetylenes in moderate to good yields. A preliminary study to gain further insight into the reaction was performed using in situ ReactIR technology.
- Stefani, Helio A.,Pena, Jesus M.,Manarin, Flavia,Ando, Romulo A.,Leal, Daiana M.,Petragnani, Nicola
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supporting information; experimental part
p. 4398 - 4401
(2011/09/19)
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- An alternative approach for the synthesis of aryl-alkyl tellurides: Reaction of aryl iodides with metal alkyltellurolates promoted by CuI
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Aryl iodides react with metal organotellurolates in tetrahydrofuran/ dimethylformamide in the presence of CuI (5 mol %) or CuI (5 mol %) and 1,10-phenanthroline (10 mol %) to afford the corresponding aryl-alkyl tellurides in good yields.
- Silva, Márcio S.,Comasseto, Jo?o V.
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supporting information; experimental part
p. 8763 - 8768
(2011/12/02)
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- Aerobic photooxidation of phosphite esters using diorganotelluride catalysts
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Diorganotellurides containing bulky aromatic substituents are found to catalyze the photooxidation of phosphite esters using aerobic oxygen as a terminal oxidant. A Hammett plot with substituted triaryl phosphites yielding p = 2.88 agrees with a nucleophilic oxygen transfer from telluroxide to phosphite.2009 American Chemical Society.
- Oba, Makoto,Okada, Yasunori,Nishiyama, Kozaburo,Ando, Wataru
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supporting information; experimental part
p. 1879 - 1881
(2009/10/10)
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- Lewis base sequestered chalcogen dihalides: Synthetic sources of ChX 2 (Ch = Se, Te; X = Cl, Br)
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The synthesis and comprehensive characterization of a series of base-stabilized ChX2 (Ch = Se, Te; X = Cl, Br) is reported using aryl-substituted diazabutadiene and 2,2'-bipyridine (bipy) as the ligands. In stark contrast to free ChX2/sub
- Dutton, Jason L.,Farrar, Gregory J.,Sgro, Michael J.,Battista, Taylor L.,Ragogna, Paul J.
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experimental part
p. 10263 - 10271
(2010/08/06)
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- Convenient synthesis of unsymmetrical organochalcogenides using organoboronic acids with dichalcogenides via cleavage of the S-S, Se-Se, or Te-Te bond by a copper catalyst
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(Chemical Equation Presented) This article describes the methodology for a copper-catalyzed preparation of numerous monochalcogenides from dichalcogenides with organoboronic acids. Unsymmetrical diorgano-monosulfides, selenides, and tellurides can be synthesized by the coupling of dichalcogenides with aryl- or alkylboronic acids using a copper catalyst in air. The present reaction can take advantage of both organochalcogenide groups on dichalcogenide.
- Taniguchi, Nobukazu
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p. 1241 - 1245
(2007/10/03)
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- Microwave-assisted copper-catalyzed preparation of diaryl chalcogenides
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Diaryl chalcogenide synthesis employing diaryl dichalcogenides and aryl halides as starting materials in the presence of excess magnesium and a catalytic amount of CuI/bipyridyl is significantly improved by microwave heating. Reaction times can be reduced from 2 to 3 days to 6-8 h. Both aryl bromides and aryl chlorides can be used as substrates in the substitution reaction. The procedure is useful not only for diaryl sulfide and diaryl selenide synthesis but also for the preparation of unsymmetrical diaryl tellurides. Starting from suitable aryl halides, the novel microwave-assisted procedure was used for the facile preparation of novel chalcogen analogues (PhS-, PhSe-, and PhTe-) of various antioxidants (ethoxyquin and 3-pyridinol). Attempts to use dialkyl dichalcogenides for the coupling of alkylchalcogeno moieties to aryl halides were only successful in the case of long-chain (such as n-octyl) disulfides and diselenides.
- Kumar, Sangit,Engman, Lars
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p. 5400 - 5403
(2007/10/03)
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- Diaryl tellurium dihalides: From Te-tetracoordinated compounds to Te-tricoordinated molecular complexes
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X-ray structural studies demonstrate that diaryl tellurium diiodides can be constrained by steric factors (ortho-alkyl substituents) to adopt a trigonal pyramidal structure in preference to the expected bisphenoidal structure. DFT calculations are shown to reproduce successfully structural details of the title compounds; they allow one to predict which coordination number should be energetically favored. All compounds are chiral, but the barrier to stereomutation by intra- and intermolecular pathways (60-85 kJmol-1) is rather low. Copyright Taylor & Francis Inc.
- Laur, Peter H.,Saberi-Niaki, Seyedeh M.,Scheiter, Michael,Hu, Chunhua,Englert, Ulli,Wang, Yuekui,Fleischhauer, Joerg
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p. 1035 - 1044
(2007/10/03)
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- Aqueous phase one-electron reduction of sulfonium, selenonium and telluronium salts
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Triorganylsulfonium, -selenonium and -telluronium salts were reduced by carbon dioxide radical anions/solvated electrons produced in aqueous solution by radiolysis. The radical expulsion accompanying reduction occurred with the expected leaving group propensities (benzyl > secondary alkyl > primary alkyl > methyl > phenyl), although greater than expected loss of the phenyl group was often observed. Diorganyl chalcogenides formed in the reductions were conveniently isolated by extraction with an organic solvent. Product yields based on the amount of reducing radicals obtained from the γ-source were often higher than stoichiometric (up to 1800 %) in the reduction of selenonium and telluronium compounds; it is likely that this result can be accounted for in terms of a chain reaction with carbon-centred radicals/formate serving as the chain transfer agent. The product distribution was essentially independent of the reducing species for diphenyl alkyl telluronium salts, whereas significant variations were seen for some of the corresponding selenonium salts. This would suggest the intermediacy of telluranyl radicals in the one-electron reduction of telluronium salts. However, pulse radiolysis experiments indicated that the lifetimes of such a species (the triphenyltelluranyl radical) would have to be less than 1 μs. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Eriksson, Per,Engman, Lars,Lind, Johan,Merenyi, Gabor
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p. 701 - 705
(2007/10/03)
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- Thermal reactions of organyl chalcogenides with α,β-unsaturated aldehydes
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Thermalgas-phase reactions of acrolein, cinnamaldehyde, and benzaldehyde with diorganyl chalcogenides and diorganyl dichalcogenides were studied.Acrolein does not react with chalcogenides at 300-600 deg C but completely decomposes under reaction conditions.At 600-650 deg C, cinnamaldehyde reacts only with diorganyl selenides and diselenides to give benzoselenophene.Its highest yield (53percent) is achieved in the reaction with dimethyl diselenide at 630 deg C and at an equimolar ratio of the reactants.The gas-phase reactions of benzaldehyde at 400-500 deg C afford chalcogen-containing derivatives of several types, among which thioanisole and its selenium or tellurium analogs predominate.The mechanisms of the above reactions were discussed in terms of homolytic substitution of the formyl group at unsaturated carbon atoms by chalcogenyl radicals. - Keywords: gas-phase reactions; cinnamaldehyde; benzaldehyde; chalcogenyl radicals; benzoselenophene, selenoanisole, telluroanisole.
- Deryagina, E. N.,Korchevin, N. A.,Shilkina, T. A.,Sukhomazova, E. N.,Levanova, E. P.
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p. 447 - 450
(2007/10/03)
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- Synthesis, spectroscopic and structural studies of O-methyl and O-isopropyl monothiocarbonate (monoxanthate) derivatives of dimethyl- and diphenyltellurium(IV). Crystal structures of Me2Te[SCO2(i-Pr)]2, Ph2Te[SCO2(i-Pr)]2, Me2TeCl[SCO2Me], and Me2TeBr[SCO2(i-Pr)]
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Monothiocarbonate derivatives of diorganotellurium(IV), R2Te[SCO2R′]2, and R2TeX[SCO2R′], where R = Me, Ph; R′ = Me, i-Pr; X = Cl, Br, and I, have been prepared and characterized by vibrational and 1H, 13C, and 125Te NMR spectroscopy. Me2Te[SCO2(i-Pr)]2 (2): P21/n (No. 14) with cell parameters a = 6.942(6) angstrom, b = 25.599(3) angstrom, c = 9.404(6) angstrom, β = 94.48(6)°, V = 1666(1) angstrom3, Z = 4, R = 0.0648, Rw = 0.0624; Ph2Te[SCO2(i-Pr)]2 (4): P21ln (No. 14) with a = 12.360(4) angstrom, b = 12.277(3) angstrom, c = 15.066(3) angstrom, β = 102.82(2)°, V = 2229.1(9) angstrom3, Z = 4, R = 0.0368, Rw 0.0312; Me2TeCl[SCO2Me] (5); P21lc (No. 14) with a = 5.193(2) angstrom, b = 18.118(4) angstrom, c = 9.613(5) angstrom, β = 91.31(6)°, V = 904.2(6) angstrom3, Z = 4, R = 0.0396, Rw = 0.0361; and Me2TeBr[SCO2(i-Pr)] (8): P21ln (No. 14) with a = 11.701(2) angstrom, b = 6.250(2) angstrom, c = 16.152(2) angstrom, β = 98.43(1)°, V = 1168.4(4) angstrom3, Z = 4, R = 0.0369, Rw = 0.0325. In all molecules, the immediate environment about tellurium is that of the saw-horse structure in which the lone pair is assumed to be stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. In 2 and 5, the terminal oxygen atoms are oriented toward tellurium, whereas in 4, one O(i-Pr) group is oriented toward tellurium, as it is in 8. In the latter cases, the terminal oxygen atoms act as weak bridges to form a pseudo dimeric species in 4 and a pseudo polymer in 8. Supramolecular interactions in 2 and 5 lead to a sulfur-bridged dimer in the former and a chlorine-bridged polymer in the latter.
- Drake,Drake,Khasrou,Mislankar,Ratnani,Yang
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p. 1968 - 1982
(2007/10/03)
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- Mild reduction of tellurium(IV) and selenium(IV) compounds by sodium ascorbate
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Sodium ascorbate was found to mildly reduce organyltellurium trihalides to diorganyl ditellurides, organylselenium trihalides to diorganyl diselenides, diorganyltellurium dihalides and oxides to diorganyl tellurides and diorganylselenium dihalides and oxides to diorganyl selenides.
- Engman,Persson
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p. 445 - 458
(2007/10/02)
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- Convenient synthesis of diaryl tellurides
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Diaryl tellurides 5 are prepared by two synthetic routes: a) a one-pot procedure using elemental tellurium (1), diethyl phosphite (2) and sodium hydride in ethanol, followed by treatment with arenediazonium fluoroborates 4; b) treatment of sodium telluride (6) with arenediazonium fluoroborates 4 in dimethylformamide. In both cases, good yields are obtained.
- Li,Lue,Zhou
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p. 281 - 283
(2007/10/02)
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- Kinetic studies on the ligand coupling reactions of tetraphenyl sulfurane, selenurane, and tellurane. Thermal stability for hypervalent chalcogen compounds with four carbon-chalcogen bonds
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Ligand coupling kinetics of tetraphenyl sulfurane, selenurane, and tellurane have been studied by the variable temperature NMR experiments. The first examples of the activation parameters for the ligand coupling (self decomposition and C-C bond formation) have been obtained for the reactions at three pentacoordinated chalcogenium centers; S, Se, Te.
- Ogawa,Sato,Furukawa
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p. 7925 - 7928
(2007/10/02)
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- A convenient method for the preparation of diaryl tellurides and diaryl selenides
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Sodium hydrogen telluride or selenide reacts rapidly with aryldiazonium fluoborates to give the corresponding symmetric diaryl tellurides or selenides.
- Chen,Qiu,Zhou
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p. 1729 - 1734
(2007/10/02)
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- SYNTHESIS, STRUCTURE, AND PROPERTIES OF COMPOUNDS WITH A CHALCOGEN-NITROGEN BOND XIII. THE EFFECT OF THE NATURE OF THE CHALCOGEN ATOM ON THE ABILITY OF N-SULFONYLCHALCOGENIMIDES TO OXIDIZE HYDROQUINONE AND ITS DERIVATIVES
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N-Sulfonyldiphenylsulfimides do not react with hydroquinone, 2,5-di(tert-butyl)hydroquinone, and tetrahydroxy-p-benzoquinone even with prolonged heating above 150 deg C.Selenimides and tellurimides with analogous structures oxidize these compounds to the corresponding quinones.The oxidizing power of the tellurimides in the investigated reations is higher than that of the selenimides.This is explained by the increased polarity of the chalcogen-nitrogen bond and, consequently, the ease of its cleavage in N-sulfonylchalcogenimides in the series: S Se Te.The intermediate products from the reaction of the tellurium derivatives with hydroquinone, i.e., polymeric diaryltellurium p-hydroxyphenolates, were isolated.
- Naddaka, V. I.,Avanesyan, K. V.,Cherkinskaya, M. L.
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p. 705 - 711
(2007/10/02)
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- Oxygen-Induced Transmetallation of Organoboranes with Diphenyl Ditelluride
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Diphenyl ditelluride rapidly reacted with trialkylboranes in the presence of oxygen to give alkyl phenyl tellurides in high yields.The facile rection proceeds via a free-radical mechanism induced by a stoichiometric amount of oxygen.A combination of this transmetallation with hydroboration provides an alternative method for hydrotelluration of olefins.
- Abe, Taro,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
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p. 1671 - 1674
(2007/10/02)
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- Electrochemically induced srn1 substitution in acetonitrile. Synthesis of arenes substituted by phenylseleno- and phenyltelluro groups
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In MeCN, the direct or mediated cathodic reduction of unactivated ArBr (Ar = 4-biphenyl, 2-fluorenyl, 9-anthryl) in the presence of an equivalent of PhE- (E = Se, Te) leads to ArEPh in interesting isolated yields (53-74 %) by SNR1 substitution. The electrochemical synthesis of 9-phenylchalcogenoanthracene proceeds in better yields in MeCN than in DMSO. The 4,4′-disubstituted biphenyl PhSeC6H4C6H4SePh was prepared in 46 % yield in MeCN whereas its synthesis by photostimulation in liquid ammonia failed.
- Degrand, Chantal
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p. 5237 - 5252
(2007/10/02)
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- A new route to seleno and telluro esters by Co2(CO)8-mediated and -catalyzed carbonylation of diaryl diselenides and ditellurides with carbon monoxide
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Diaryl Diselenides react with CO(5-100 atm) at 100-200°C during 1-4 h in the presence of Co2(CO)8 to give the corresponding aryl selenocarboxylic acid esters in 21-96% yields. Similar treatment of diphenyl ditelluride gives the telluro analogues in lower yields. Didodecyl diselenide also gives the corresponding seleno ester, while esters were not produced from dibenzyl diselenide and didodecyl ditelluride. Under milder conditions (10 atm CO/125°C/1 h) the reactivity of (PhM)2 (M S, Se, Te) for the corresponding esters was found to be in the order Te > Se > S. The carbonylation of diaryl diselenides proceeds catalytically in Co2(CO)8 in the presence of triphenylphosphine. It was shown unambiguously that benzoylcobalt tetracarbonyl, which is one of the possible intermediates when aryl is phenyl, reacts smoothly with diphenyl diselenide or ditellutide to give the corresponding ester, phenyl selenobenzoate or tellurobenzoate, respectively, in a good yield.
- Uemura, Sakae,Takahashi, Hidetaka,Ohe, Kouichi,Sugita, Nobuyuki
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- DIORGANOTELLURBIS(ALKYLXANTHOGENATE), TEIL II
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Diphenyltelluriumbis(alkylxanthates) as well as telluracyclopentane-1,1-bis(alkylxanthates) of the general formula R2Te(S2COR')2 and C4H8Te(S2COR')2 (R = C6H5 and R' = CH3, C2H5, i-C3H7) are obtained by reaction of diphenyltellurium-dichloride or telluracyclopentane-1,1-diiodide with sodiumxanthates.The insertion of CS2 into the corresponding organotelluriumbis-alkoxydes is only successful in the case of the cyclic compound.Diphenyltelluriumbis-alkoxydes react with decomposition.This decomposition in substance and in solution is investigated.
- Wieber, Markus,Schmidt, Elmar
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p. 223 - 228
(2007/10/02)
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- SYNTHESIS, STRUCTURE, AND PROPERTIES OF COMPOUNDS WITH A CHALCOGEN-NITROGEN BOND. X. REACTION OF TELLURIMIDES WITH THIOLS AND THIOAMIDES
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Tellurimides readily oxidize thiophenol and benzyl hydrogen sulfide at room temperature to the corresponding disulfides, thiourea to cyanamide, thiobenzamide to benzonitrile, and 1,3-diphenylthiourea to diphenylcarbodiimide.
- Naddaka, V. I.,Avenesyan, K. V.,Cherkinskaya, M. L.,Minkin, V. I.
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p. 1426 - 1429
(2007/10/02)
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- Application of phosphine tellurides to the preparation of group II-VI (2-16) semiconductor materials
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In order to find low-temperature routes to metal tellurides, we have investigated some of the reactions of phosphine tellurides. Via the phosphine telluride, tellurium is chemically transported by PMe3 under very mild conditions (T ≈ 150°C). Triethylphosphine telluride reacts with Hg at room temperature and with HgR2 (R = Et, Ph) at 115°C, in each case giving HgTe as the sole solid-state product. We studied the reaction with HgPh2 in greater detail, showing that Ph2Te and Ph2Te2 are the major organic products.
- Steigerwald,Sprinkle
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p. 245 - 246
(2008/10/08)
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