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The possibilities and limitations of 13C NMR spectroscopy for the determination of the basicity of carbonyl-containing compounds are examined.It is shown that the protonation of polycyclic aromatic ketones in deutero acids increases the contribition of the C+-OD form relative to that of the C=+OD form, whereas in the case of aliphatic ketones and of monosubstituted acetophenones and benzaldehydes the C=+OD form is predominant.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Phosphazene bases have been utilized as efficient organocatalysts to catalyze the double Michael additions of divinyl ketones with active methylenes to afford functionalized cyclohexanones in 36-91% yields with >25:1 diastereoselectivity.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A serie of substituted amines based ionic liquids was prepared using an aliphatic linear carboxylic acid (pentanoic acid). The ionic liquids synthesised are 2-hydroxy ethylammonium pentanoate (2-HEAPE), 2-hydroxy diethylammonium pentanoate (2-HDEAPE) and 2-hydroxy triethylammonium pentanoate (2-HTEAPE). FT-IR spectra establishes their ionic salt structure. The influence of structural variations on their thermodynamic properties (density, ultrasonic velocity, ionic conductivity, refractive index, viscosity and surface tension) was investigated, as a function of temperature in the range 278.15-338.15. K. In the compounds studied here, the anion has strong effect on the properties if compared with previous studies of the authors, when shorter chains were used. It was found that the elongation of the alkyl chain causes the pronounced depression of fluidity and ionic conductivity. The observed temperature trend of the studied properties points out the special packing of these ionic liquids, as well as, the strong influence of the steric hindrance among linear aliphatic residues. We also describe the catalytic activity of these type of ionic liquids for a representative serie of aldol condensation processes. Conversions higher than 98% and selectivities higher than 85% were obtained. Moreover the catalysts are easily separated from reaction mixture and re-used, obtaining good conversions for at least three consecutive cycles. As a conclusion, it was found that simple structural modifications into anion length and degree of substitution provide a mechanism to manipulate the catalytic potency of these ionic liquids, as well as, tailor physico-chemical properties for potential end-use applications.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A Pd(0)-catalyzed Hiyama coupling reaction of tetrafluoroethylene (TFE) proceeded without the use of a base to give alpha,beta,beta- trifluorostyrene derivatives. A Ni(0)-catalyzed Hiyama coupling reaction of perfluoroarenes also occurred without a base. The key intermediate in these reactions would be a transition-metal fluoride complex that is generated in situ by the oxidative addition of a C-F bond.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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1,5-Diphenyl-1,4-pentadien-3-oxime (DPPDO) has been identified as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). This reagent reacts with copper(II) in the pH range of 2.0-12.0 to form a yellowish-red 1:1 complex in chloroform with a absorbante maximum at 503 nm having molar absorptivity and Sandell’s Sensitivity values of 1.57 × 104 mol-1 cm-1 and 0.004065 mug cm-2 respectively. The developed extractive spectrophotometric method has successfully been employed for the determination of CuII in leafy vegetables etc.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Palladium(0)-dibenzylidene acetone complexes Pdx(dba)y, with y/x being from 1.5 to 3, are provided according to the invention at a purity of at least 99.5 wt. %. The use of said Pdx(dba)y complexes according to the invention is for determining their stoichiometry by means of elemental analysis. In the method for the production of Pdx(dba)y complexes from a Pd-containing educt and dibenzylidene acetone (dba) in alcohol, according to the invention a solution of the dba in alcohol pre-heated to more than 40 C. is provided first and then the Pd-containing educt is added to the pre-heated solution upon which the complexes are precipitated by a base.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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2,3-Dihydro-1H-1,5-benzodiazepines have been prepared in good yield by reaction of o-nitroanilines with chalcones induced by the TiCl4-Sm-THF system under mild reaction conditions.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A new and practical method for the efficient chlorination of tertiary, secondary, and primary benzylic and allylic alcohols is described. The method is characterized by the formation of hydrogen chloride from trimethylsilyl chloride and trace water, the formation of a carbenium ion through the protonation of an alcohol and subsequent dehydration, and the chlorination of the carbenium ion. During the process, sodium ion-exchanged montmorillonite plays a crucial role in capturing the generated hydrogen chloride, stabilizing the carbenium intermediate as well as promoting the chlorination.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Polypyrrole stabilised palladium nanoparticles show good catalytic efficiency for the chemoselective transfer hydrogenation of alpha,beta- unsaturated carbonyl compounds. The catalyst is very specific and selectively hydrogenates the olefins or acetylenes only, without affecting the carbonyl moiety, with an excellent yield of products for a wide range of substrates. Podium position for palladium: A palladium-polypyrrole composite is synthesized for the chemoselective transfer hydrogenation of alpha,beta-unsaturated carbonyl compounds by using an in situ polymerisation and composite formation method. No semi-hydrogenated product was observed with alkyne systems and hydrodehalogenation of the haloarene segment of the substrate was not encountered in reactions with this catalyst.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Under basic catalysis conditions the reaction of 4- and 4′-substituted chalcones with o-phenylenediamine leads to 2,3-dihydro-2,4-diaryl-1H-1,5-benzodiazepines; beta-amino adducts, the ability of which to undergo intramolecular condensation increases as the basicity of the catalyst is increased, are formed as intermediates.A different pathway for the process (the formation of an azomethine) is observed in the reaction with cinnamaldehyde.It is concluded that conformational factors play a primary role in the direction of the reaction.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate