Search results for "TRIF"
showing 10 items of 1419 documents
Star-Shaped Compounds Having 1,3,5-Triazine Cores
2003
The 1,3,5-triazine derivatives 1−4 having styryl or higher oligo(phenylenevinylene) chains in the 2-, 4-, and 6-positions represent star-shaped push-pull compounds. Alkoxy or dimethylamino groups on the peripheral benzene rings, which act as electron donors, and the central 1,3,5-triazine ring, which acts as an electron acceptor, cause intramolecular charge transfer (ICT) to occur in the absorption S0⇄S1. Protonation of the 1,3,5-triazine core enhances the effect, as demonstrated by a bathochromic shift; a secondary protonation on the dimethylamino groups, however, leads to the breakdown of the ICT. Thus, the yellow compound 1d first becomes violet and then colorless upon the addition of tr…
Self-Assembly, Characterisation, and Crystal Structure of Multinuclear Metal Complexes of the [2×3] and [3×3] Grid-Type
2002
The self-assembly of new multimetallic complexes of grid-type architecture is described. The binding of a set of tris-terdentate ligands, 1 a-1 d, based on terpyridine-like subunits, with different octahedrally coordinated metal ions leads to the formation of species whose structure depends strongly on the ligand, the metal ion, the counterion, the solvent, and the reaction conditions. Under suitable conditions, the [3 x 3] grid was obtained from the reaction of ligand 1 a with zinc tetrafluoroborate and from ligand 1 b with mercury triflate. The other ligands led to the formation of mainly one compound of composition [M(6)L(5)](12+), which has the structure of an incomplete [2 x 3] grid. T…
Synthesis of nonracemic α-trifluoromethyl α-amino acids from sulfinimines of trifluoropyruvate
2001
We describe a novel and useful method for the synthesis of nonracemic α-trifluoromethyl α-amino acids (α-Tfm-AAs). Key building blocks are the sulfinimines (S)-1a and (S)-1b, prepared by Staudinger reaction from trifluoropyruvate esters and the chiral N-sulfinyl iminophosphorane (S)-8, which were treated with benzyl, allyl, and alkylmagnesium halides. The resulting diastereomeric N-sulfinyl α-Tfm α-amino esters, 12 and 13, were produced with moderate to good stereoselectivity and yields. When alkyl Grignard reagents were used, stereocontrol became progressively higher with increasing steric bulk, while reversed, though poor, stereocontrol was achieved with benzyl/allyl Grignard reagents. An…
Biogas Cleaning by Hydrogen Sulfide Scrubbing and Bio-oxidation of Captured Sulfides
2015
Hydrogen sulfide and partially carbon dioxide can be absorbed into alkaline washing liquid with nitrates for upgrading a quality of biogas. Sulfides captured into the washing liquid are consequently biologically oxidized in an anoxic bioreactor by autotrophic denitrifying bacteria. Nitrates in the washing liquid serve as electron acceptors for sulfide bio-oxidation. Washing of hydrogen sulfide from biogas was examined in a lab-scale countercurrent scrubber that was packed with plastic carriers and operated at different biogas and washing liquid flows. The hydrogen sulfide concentration in treated biogas was investigated in the range from 3 to 12.3 g m–3. The influence of the hydrogen sulfid…
Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts.
2004
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 p…
DESASS: A software tool for designing, simulating and optimising WWTPs
2008
This paper presents a very useful software tool to design, simulate and optimise wastewater treatment plants. The program is called DESASS (DEsign and Simulation of Activated Sludge Systems) and has been developed by CALAGUA research group. The mathematical model implemented is the Biological Nutrient Removal Model No.1 (BNRM1) which allows simulating the most important physical, chemical and biological processes taking place in treatment plants. DESASS calculates the performance under steady or transient state of whole treatment schemes including primary settlers, volatile fatty acid generation systems by primary sludge fermentation, activated sludge systems for biological organic matter a…
Asymmetric synthesis of polycyclic 3-fluoroalkylproline derivatives by intramolecular azomethine ylide cycloaddition
2019
The asymmetric synthesis of polycyclic fluorinated proline derivatives has been accomplished by means of an intramolecular azomethine ylide cycloaddition with fluorinated dipolarophiles. Thus, the reaction of benzaldehydes bearing a trifluoromethyl alkene in ortho position with an azomethine ylide precursor derived from chiral 2-amino indanol takes place with excellent levels of diastereoselectivity, with simultaneous generation of four stereocenters. In order to determine the influence of the fluorine moiety in the process, starting material bearing non-fluorinated alkenes were synthesised. In this case, a dramatic drop of selectivity occurred, which indicates that the role of the fluorine…
Reaction of lithium enediolates with perfluoroketene dithioacetals. Synthesis of α-trifluoromethyl γ-dicarboxylic acid derivatives
2004
The reaction of perfluoroketene dithioacetals with dianions of carboxylic acids proceeds through the substitution of the vinylic fluoride. The preparative value of this reaction depends strongly on the reaction and work-up conditions, the optimisation of which led to use LDA as a base and multiple extraction techniques. The overall process may be considered as a formal synthesis of α-trifluoromethyl γ-dicarboxylic acid derivatives.
The role of the trifluoromethyl group in reactivity and selectivity in polar cycloaddition reactions. A DFT study
2012
Abstract The role of the trifluoromethyl group in reactivity, regio-, and stereoselectivity in cycloaddition reactions has been analyzed by studying the 1,3-dipolar cycloaddition (13DC) reactions of nitrone 4 with 3,3,3-trifluoro-1-nitropropene 7b and 3,3,3-trifluoro-2-nitropropene 14 using density functional theory (DFT) methods at the B3LYP/6-311G(d) level. The recent M06-2X functional has also been evaluated but, although the thermodynamic performance is improved, the kinetic data are not necessarily better than those obtained by the popular B3LYP functional for cycloaddition reactions. Four reactive channels associated with the meta and ortho regio- and endo and exo stereoselective appr…
Stereoselective synthesis of unsaturated and functionalized L-NHBoc amino acids, using Wittig reaction under mild phase-transfer conditions.
2012
The stereoselective synthesis of a new amino acid phosphonium salt was described by quaternization of melting triphenylphosphine with the γ-iodo NHBoc-amino ester, derived from L-aspartic acid. The deprotection of the carboxylic acid function to afford the phosphonium salt with a free carboxylic acid group was achieved by a palladium-catalyzed desallylation reaction. This phosphonium salt was used in the Wittig reaction with aromatic or aliphatic aldehydes and trifluoroacetophenone, under solid-liquid phase-transfer conditions in chlorobenzene and in the presence of K(3)PO(4) as weak base, to afford the corresponding unsaturated amino acids without racemization. Thus, the reaction with subs…