Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.     

KMo5O13 and KNb1.76Sb3.24O13

The title compounds, potassium pentamolybdenum oxide, KMo₅O₁₃, and potassium niobate antimonate or potassium niobium antimony oxide (1/1.76/3.24), KNb_1.76Sb_3.24O₁₃, were synthesized by solid‐state reactions and are isomorphous in space group Cmcm. The structure of the Mo complex has three unique Mo atoms and consists of MoO₆ octahedra sharing edges to form Mo₂O₆ pairs and Mo₃O₉ triplets, which, in turn, form layers by sharing corners. These layers are linked together in the [100] direction, yielding a three‐dimensional network similar to that of KSb₅O₁₃. This framework delimits interconnected tunnels, running approximately along the [110] and [10] directions, in which K⁺ ions are located. In the isomorphous KNb_1.76Sb_3.24O₁₃ structure, one of the Mo sites in KMo₅O₁₃ is replaced by Sb and the other two Mo sites have been replaced by Nb/Sb.     

A novel and efficient method for the synthesis of α-aminonitriles by the reaction of aminals with trimethylsilyl cyanide catalyzed by iodine

Iodine, was found to be a practical and novel catalyst for the reaction of aminal and trimethylsilyl cyanide under mild and neutral reaction condition to afford the corresponding α-aminonitriles in high yields and short reaction times. Trimethylsilyl iodide derived in situ from elemental iodine and trimethylsillyl cyanide catalyzed this conversion.     

SUPPRESSION OF THE INDUCTION OF DELAYED-TYPE HYPERSENSITIVITY REACTIONS IN MICE BY A SINGLE EXPOSURE TO ULTRAVIOLET RADIATION

Abstract— After a single exposure of mice to UV radiation, their ability to generate a contact hypersensitivity (CHS) response to contact sensitizers applied epicutaneously to distant, unirradiated skin is severely impaired. It is not clear, however, if the classic delayed type hypersensitivity (DTH) reponse to exogenous antigens, injected into the subcutaneous (s.c.) space, can also be modulated by UV radiation. We report here that a single exposure of mice to UV radiation suppressed the induction of DTH to both erythrocyte and soluble protein antigens injected s.c., but did not suppress the elicitation of the response. The suppressive effect was abrogated by cyclophosphamide treatment. In addition, antigen-specific suppressor cells were found in the spleens of the mice with a decreased DTH response. Since the ability to mount a DTH response has been linked with the resistance to certain pathogenic microorganisms, we suggest that the suppression of DTH by UV radiation may have the potential to compromise host resistance to such infectious agents.     

Influence of the halogen ligand on the near-UV-visible spectrum of [Ru(X)(Me)(CO)2(alpha-diimine)] (X = Cl, I; alpha-diimine = Me-DAB, iPr-DAB; DAB = 1,4-diaza-1,3-butadiene): an ab initio and TD-DFT analysis

The near-UV-vis electronic spectroscopy of [Ru(X)(Me)(CO)(2)(iPr-DAB)] (X = Cl or I; iPr-DAB = N,N'-di-isopropyl-1,4-diaza-1,3-butadiene) is investigated through CASSCF/CASPT2 and TD-DFT calculations on the model complexes [Ru(X)(Me)(CO)(2)(Me-DAB)] (X = Cl or I). Convergence of the calculated transition energies for the low-lying metal-to-ligand charge-transfer (MLCT), X-to-ligand charge-transfer (XLCT, X halide ligand), or sigma-bond-to-ligand charge-transfer (SBLCT) to experimental values is analyzed for both methods. On the basis of these accurate calculations, it is shown that whereas the lowest singlet state can be assigned to a nearly pure XLCT state in [Ru(I)(Me)(CO)(2)(Me-DAB)], its character is mainly MLCT in [Ru(Cl)(Me)(CO)(2)(Me-DAB)]. These results are in agreement with time-resolved emission/IR and resonance Raman experimental data. The experimental UV-vis bands are well reproduced by the CASSCF/CASPT2 calculations. The TD-DFT transition energies to the long-range charge transfer states are dramatically affected by the nature of the functional, with lowering leading to meaningless values in the case of nonhybrid functionals. Both methods reproduce well the red shift of the absorption bands on going from the chloride to the iodide complex as well as the shift of the strongly absorbing higher MLCT transition from the visible to the UV domain of energy.     

Synthetic Strategies To Obtain V-P-O Open Frameworks Containing Organic Species as Structural Directing Agents. Crystal Structure of the V(IV)-Fe(III) Bimetallic Phosphate [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)][Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O

A general synthetic approach to rationalize the solution preparative chemistry of oxovanadium phosphates containing organic species as structural directing agents is presented. Careful attention is payed to the hydrolysis and condensation processes involving the ionic species in solution, and a simple restatement of the partial charge model (PCM) has been used in order to organize the experimental results. The structure of a new V(IV)-Fe(III) bimetallic oxovanadium phosphate, [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)] [Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O, has been determined by X-ray single crystal diffraction methods. This compound crystallizes in the monoclinic system, space group P2(1)/n and the cell dimensions are as follows: a = 14.383(3) ?, b = 10.150(2) ?, c = 18.355(4) ?, and beta = 90.39(3) degrees (Z = 2). The existence of a complex intercrossing channel system, including a very large channel of 18.4 ? of diameter (in which both water molecules and ethylenediamine species are located), is the more interesting feature of this structure. Thermal decomposition, including the dehydration/rehydration process, has been studied by thermal analysis and variable temperature X-ray powder diffraction techniques. A complementary SEM study of the different intermediate decomposition products is presented.     

Crystal Structure of a New Ammonium Potassium Selenomolybdate Compound K3.31(NH4)0.69[Se2Mo5O21]·2H2O

An inorganic compound formulated as K_3.31(NH₄)_0.69[Se₂Mo₅O₂₁]·2H₂O has been synthesized by conventional solution method and characterized by scanning electron microscopy, IR, UV-Vis spectroscopies behaviors. The structure of the title compound has been determined from a single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁/n, with a?=?9.9371(2) ?, b?=?23.3545(2) ?, c?=?10.5179(2) ?, β?=?114.12(3)°, V?=?2227.7(5) ?³ and Z?=?4. It was revealed that the Strandberg-type polyoxoselenomolybdate cluster can be considered as a ring formed by five distorted edge- and corner-sharing MoO₆ octahedra, capped on both poles by a selenate pyramids sharing three vertices with the ring molybdenum centers. The Strandberg clusters are connected with ammonium ions and water molecules through hydrogen-bonding interactions which ensure the cohesion of the structure into a three-dimensional network.     

Multicomponent reaction in deep eutectic solvent for synthesis of substituted 1-aminoalkyl-2-naphthols

Research on Chemical Intermediates - One-pot multicomponent synthesis of Betti bases (aminoalkyl naphthols) from aldehydes, β-naphthol, and secondary amines in deep eutectic solvent (DES)...