- Mono- And Dinuclear α-Diimine Nickel(II) and Palladium(II) Complexes in C-S Cross-Coupling
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The usefulness of transition metal catalytic systems in C-S cross-coupling reactions is significantly reduced by air and moisture sensitivity, as well as harsh reaction conditions. Herein, we report four highly air- and moisture-stable well-defined mononuclear and bridged dinuclear α-diimine Ni(II) and Pd(II) complexes for C-S cross-coupling. Various ligand frameworks, including acenaphthene- and iminopyridine-based ligands, were employed, and the resulting steric properties of the catalysts were evaluated and correlated with reaction outcomes. Under aerobic conditions and low temperatures, both Ni and Pd systems exhibited broader substrate scope and functional group tolerance than previously reported catalysts. Over 40 compounds were synthesized from thiols containing alkyl, benzyl, and heteroaryl groups. Also, pharmaceutically active heteroaryl moieties are incorporated from thiol and halide sources. Notably, the bridged dinuclear five-coordinate Ni complex has outperformed the remaining three mono four- or six-coordinate complexes by giving almost quantitative yields across a broad substrate scope.
- Talukder, Md Muktadir,Miller, Justin T.,Cue, John Michael O.,Udamulle, Chinthaka M.,Bhadran, Abhi,Biewer, Michael C.,Stefan, Mihaela C.
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- One-Pot Copper-Catalysed Thioetherification of Aryl Halides Using Alcohols and Lawesson's Reagent in Diglyme
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A new protocol for the thioetherification of structurally varied alcohols with aryl halides using Lawesson's reagent, catalysed by copper(I) iodide, and using diglyme as a safe solvent was developed. Using this method, the reactions of aryl halides proceeded efficiently, and the desired sulfides were obtained in high to excellent yields. The method uses alcohols as starting materials, which is a significant advantage over methods that start from thiols. Alcohols are widely commercially available in a much greater structural diversity than thiols, and they are also nontoxic and not foul-smelling. A reaction mechanism was proposed. A copper-catalysed method for the thioetherification of alcohols with aryl halides using Lawesson's reagent was developed.
- Gholinejad, Mohammad
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p. 4162 - 4167
(2015/06/30)
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- Synthesis and characterization of magnetic copper ferrite nanoparticles and their catalytic performance in one-pot odorless carbon-sulfur bond formation reactions
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In this article, we have introduced catalytic application of copper ferrite nanoparticles (CuFe2O4) for one-pot odorless production of aryl alkyl thioethers using thiourea and alkyl bromides in wet polyethylene glycol as a green solvent. The catalyst was also successfully applied for one-pot synthesis of symmetrical diaryl trithiocarbonates via the reaction of sodium sulfide, carbon disulfide and aryl iodides under heterogeneous reaction condition. Magnetic copper ferrite nanoparticles were synthesized using iron (III) chloride and copper (II) chloride, and characterized using XRD, FT-IR, AAS, and TEM analysis. The catalyst was recycled using simple magnetic separation and reused for the five consecutive runs in the reaction of iodobenzene, thiourea and benzyl bromide without appreciable loss of activity.
- Gholinejad, Mohammad,Karimi, Babak,Mansouri, Fariborz
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- ANTHRAPYRIDONE COMPOUND OR SALT THEREOF, MAGENTA INK COMPOSITION CONTAINING THE ANTHRAPYRIDONE COMPOUND, AND COLORED BODY
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The present invention relates to a novel anthrapyridone compound represented by the following formula (1) or a salt thereof: [wherein, R1 represents a hydrogen atom, an alkyl group or the like, R2 represents a hydrogen atom or a methoxy group and R3 represents an unsubstituted or substituted C5-C12 alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, respectively; and with regard to the substitution positions of -SO2R3 and -SO3H whose substitution position are not specified and the both of which the benzene ring has thereon, one of their substitution positions is the para-position and the other thereof is the ortho-position to the substitution position of the nitrogen atom by which said benzene ring is substituted], and the compound of the present invention or a salt thereof has a hue which possesses high vividness suitable for inkjet recording, and provides a magenta coloring matter having higher fastnesses on recorded matter and excellent storage stability.
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Page/Page column 17
(2010/11/04)
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- Synthesis of 4-nitrophenyl sulfones and application in the modified Julia olefination
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4-Nitrophenyl (NP) sulfones have been successfully employed in the modified Julia olefination reaction with carbonyl compounds. The olefination reaction proceeds through a sequence of aldol addition, Smiles rearrangement, and elimination. The sulfones are easily prepared in high yields in a two-step sequence starting from inexpensive commercially available para- fluoronitrobenzenes via nucleophilic aromatic substitution by a mercaptane and subsequent oxidation under standard conditions. The modified Julia reaction between NP sulfones and a wide variety of aromatic aldehydes affords the corresponding styrenes, stilbenes and cinnamate derivatives in yields up to 97% and good stereoselectivities. A mechanistic rationale is advanced to explain the observed results. Georg Thieme Verlag Stuttgart.
- Mirk, Daniela,Grassot, Jean-Marie,Zhu, Jieping
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p. 1255 - 1259
(2007/10/03)
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- Synthesis and in vitro antifungal activity of 4-substituted phenylguanidinium salts
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A series of 4-substituted phenylguanidinium derivatives was synthesized and its antimicrobial activity was evaluated in vitro against eight potentially pathogenic strains of fungi.
- Braunerova, Gabriela,Buchta, Vladimir,Silva, Luis,Kunes, Jiri,Palat Jr., Karel
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p. 443 - 450
(2007/10/03)
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- Photooxidation of alkyl 4-nitrophenyl sulfides and sulfoxides. Observation of oxidative C-S bond cleavage and rearrangement reactions
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Alkyl 4-nitrophenyl sulfides and sulfoxides undergo a self-photoinduced, singlet oxygen oxidation to produce a variety of products, including sulfonates and carbonyl compounds formed by the oxidative cleavage of the C-S bond of the sulfides and sulfoxides. Structural rearrangements are observed in the resulting carbonyl compounds formed in the oxidative cleavage of the C-S bond in the tert-amyl and 2-phenylethyl sulfides. An overall mechanism is proposed which involves the formation of peroxysulfoxides and peroxysulfones which undergo heterolytic C-S bond cleavage to form ion pairs which recombine to form persulfenates or persulfinates which then undergo photo- and/or thermallyinduced homolytic O-O bond cleavage to form alkoxy and sulfinyl or sulfonyl radicals. The alkoxy radicals undergo β-scission, disproportionation, or recombination with the sulfonyl radical to form the observed products. These C-S oxidative cleavage reactions have only been rarely observed in the earlier studies on the singlet oxygen oxidation studies of dialkyl sulfides, and are attributed, in part, to the presence of the 4-nitro group on the aromatic ring which greatly affects the susceptibility of the sulfur atom of the sulfides and sulfoxides toward nucleophilic attack, and on the reactivity of the peroxysulfoxides and peroxysulfones toward heterolytic cleavage of the O-S bond.
- Pasto, Daniel J.,Cottard, Fran?ois,Jumelle, Laurent
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p. 8978 - 8984
(2007/10/02)
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