N,N,N,N-Tetramethyl-1,3-propanediamine as the catalyst of choice for the Baylis-Hillman reaction of cycloalkenone: rate acceleration by stabilizing the zwitterionic intermediate via the ion-dipole interaction

N,N,N^′,N^′-Tetramethyl-1,3-propanediamine (TMPDA) can be used as an efficient catalyst for the Baylis-Hillman reaction of cycloalkenones. The increased reaction rate was thought be derived from the stabilizing effect of the zwitterionic intermediate via the ion-dipole interaction.     

Preparation, Characterization and Catalytic Performance of La-SO4/SBA-15 in Esterification of Acetic Acid with n-Butanol

La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.     

Effects of partial anion substitution on the thermoelectric properties of silver(I) chalcogenide halides in the system Ag5Q2X with Q=Te, Se and S and X=Br and Cl

A selection of mixed conducting silver chalcogenide halides of the general formula Ag₅Q₂X with Q=sulfur, selenium and tellurium and X=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag₅Te₂Cl showed a defined d¹⁰-d¹⁰ interaction in the disordered cation substructure at elevated temperatures where Ag₅Te₂Cl is present in its high temperature α-phase. A significant drop of the thermal diffusivity has been observed during the β−α phase transition reducing the values from 0.12 close to 0.08 mm² s⁻¹. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values.Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag₅Q₂X were determined around the silver-order/disorder β−α phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the β−α phase transition. Thermal conductivities are low reaching values around 0.2-0.3 W m⁻¹ K⁻¹ at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag₅Q₂X phases.     

Synthesis and characterization of 9-methyl-2-morpholin-4-yl-8-substituted phenyl-1H-purine derivatives using polyphosphoric acid (PPA) as an efficient catalyst

We demonstrate the synthesis of various purine derivatives through the coupling of N⁴-methyl-2-morpholin-4-yl-pyrimidine-4,5-diamine with various aldehydes by using polyphosphoric acid (PPA) as an efficient catalyst in DMF at reflux temperature. The PPA catalyst gave better yields (70-85%) in short reaction times (45-60 min). This commercially available cheap catalyst is more active than many reported expensive catalysts. Many aldehydes underwent the above conversion to form a series of 9-methyl-2-morpholin-4-yl-8-phenyl-9H-purines.     

A N NMR study of tautomerism in dimethyl dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate

Dimethyl dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate can exist either in 1,2- or 1,4-dihydro tautomeric forms. The ¹⁵N NMR spectra of dimethyl dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate were measured at the ¹⁵N natural abundance level as well as in ¹⁵N doubly labelled selectively and in ¹⁵N completely labelled compounds (20% ¹⁵N). The J(¹⁵N,¹⁵N) value was determined in ¹⁵N completely labelled compounds (20% ¹⁵N) using 1D ¹⁵N INADEQUATE and was found to be 12.2 ± 0.2 Hz in deuteriochloroform, acetonitrile-d₃, DMSO-d₆ and CD₃OH. Very similar ¹⁵N chemical shifts and ¹J(¹⁵N,¹H) values were also observed in all the solvents. This indicates that compound 1 exists completely in the 1,4-dihydro tautomeric form (i.e., as dimethyl 1,4-dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate) in all the solvents tested.     

High power impulse magnetron sputtering (HIPIMS) and traditional pulsed sputtering (DCMSP) Ag-surfaces leading to E. coli inactivation

This study addresses the high power impulse magnetron sputtering (HIPIMS) deposition of Ag-nanoparticle films on polyester and the comparison with films deposited by direct current pulsed magnetron sputtering (DCMSP). The first evidence is presented for the Escherichia coli bacterial inactivation by HIPIMS sputtered polyester compared to Ag-polyester sputtered by DCMSP. HIPIMS layers were significantly thinner than the DCMSP sputtered layers needing a much lower Ag-loading to inactivate E. coli within the same time scale. The Ag-nanoparticle films sputtered by DCMSP at 300 mA for 160 s was observed to inactivate completely E. coli within 2 h having a content of 0.205% Ag wt%/polyester wt%. HIPIMS-sputtered at 5 A for 75 s led to complete E. coli bacterial inactivation also within 2 h having a content Ag 0.031% Ag wt%/polyester wt%. The atomic rate of deposition with DCMSP is 6.2 × 10¹⁵ atoms Ag/cm² s while with HPIMS this rate was 2.7 × 10¹⁵ atoms Ag/cm² s. The degree of ionization of Ag⁺/Ag²⁺ and Ar⁺/Ar²⁺ was proportional to the target current applied during HIPIMS-sputtering as determined by mass spectroscopy. These experiments reveal significant differences at the higher end of the currents applied during HIPIMS sputtering as illustrated by the ion-flux composition. X-ray photoelectron spectroscopy (XPS) was used to determine the surface atomic concentration of O, Ag, and C on the Ag-polyester. These surface atomic concentrations were followed during the E. coli inactivation time providing the evidence for the E. coli oxidation on the Ag-polyester. X-ray diffraction shows Ag-metallic character for DCMSP sputtered samples for longer times compared to the Ag-clusters sputtered by HIPIMS leading to Ag-clusters aggregates. Ag-nanoparticle films on polyester sputtered by HIPIMS contain less Ag and are thinner compared to Ag-nanoparticle films sputtered by DCMSP.     

Using Ozawa method to study the curing kinetics of electrically conductive adhesives

In this paper, we fabricated electrically conductive adhesives using vinyl ester resin and micro silver flakes, and then cured the adhesives by heat without any catalysts or initiators. The curing temperature was above 200 °C, and the curing time about 30 min. Under these heat curing conditions, the double bonds in the adhesives reached a high conversion (α) around 98.88 % calculated from the Fourier transform infrared spectroscopy analysis. The curing kinetics of heat curing products was studied using Ozawa method and deduced by assuming a constant activation energy (E). The curing kinetic equation was obtained as dα/dt = e^17.70(1 ? α)^1.19 α ^0.41e^(?94.32)/RT) with E = 94.32 kJ mol^?1. The heat curing followed the shrinking core model from the resin-particle system. The data calculated from the kinetic equation agreed well with the experimental data, showing that the Ozawa method could evaluate the curing kinetics effectively. Furthermore, a comprehensive and in-depth understanding of the curing kinetics of heat curing electrically conductive adhesives has been achieved with this Ozawa method.     

A kinetic investigation of removal of chromium from aqueous solutions with a strong cation exchange resin

A kinetic investigation was performed with an ion exchange resin for chromium. A strong cation exchange resin (Amberlite IR 120) was used for removal of chromium. The effects of concentration, resin amount, and stirring speed on kinetics were investigated. The metal concentration range studied was between 5 to 160 mg/dm³ (the amount of solution was 4 dm³), the resin amount range was between 5 to 20 mg, and the stirring speed range was between 1000 to 3500 rpm. Equilibrium experiments were performed for calculation of separation factor. Kinetic studies were done using a Kressman-Kitchener stirrer reactor system and the results were compared with existing kinetic models. Two models, Nernst-Plank film diffusion control model (fdc) and solid phase diffusion control model (pdc), respectively were identified, and the dependence of the rate on parameters such as solution concentration, resin amount, stirring speed, etc. was examined for each of them. The interpretation of these data shows that the system is probably controlled by both film and particle diffusion. Correspondence: Sevgi Kocaoba, Department of Chemistry, Faculty of Art and Science, Yildiz Technical University, Davutpasa Cad. No: 127, 34210 Davutpasa-Istanbul, Turkey.     

P NMR study of the stoichiometry, stability and thermodynamics of new complexation between uranyl (II) nitrate and N-methyliminobis(methylenephosphonic acid) in two binary D2O-DMSO-d6 solvent mixtures

The complexation reaction between uranyl (II) nitrate, and N-methyliminobis(methylenephosphonic acid) (MIDPH) was investigated in two different binary solvent mixtures of D₂O-DMSO-d₆ at various temperatures using ³¹P NMR spectroscopy. The exchange between the free ligand and the 1:1 complexed ligand was slow on the NMR timescale and two ³¹P NMR signals were observed. The formation constant of the resulting complex was evaluated from integration of the two ³¹P NMR signals. The values of thermodynamic parameters of the resulting complex (ΔH, ΔS and ΔG) were determined from the temperature dependence of the formation constants. In the two solvent mixtures studied, the resulting complex is enthalpy stabilized but entropy destabilized.     

Effect of alkylresorcinols on curing behaviour of phenol-formaldehyde resol resin

Thermal behaviour of cure-accelerated phenol-formaldehyde (PF) resins was studied using the addition of commercial mixture of water soluble oil shale alkylresorcinols (AR) to PF resin, 5-MR being as model compound. The acceleration effect of AR is based on the promotion of condensation of resin methylol groups and subsequent reaction of released formaldehyde with AR. Commercial PF resins SFŽ-3013VL and SFŽ-3014 from the Estonian factory VKG Resins have been used. The chemical structure of resins was characterised by ¹³C NMR spectroscopy. TG-DTA analysis was carried out using labsys^TM instrument Setaram. By TG-DTA measurements, the shift of exothermic and endothermic peaks and the changes of mass loss rate in the ranges of 1.5–10 g AR/100 g PF resin were studied. The effect of AR on the curing behaviour of PF resins was also followed by gel time. Testing of the plywood when using PF resin with 5 mass% of AR shows that the press time could be reduced by about 15%.     

Baseline isotopic data of polyhalogenated compounds

The δ²H- and δ¹³C-values of polyhalogenated compounds were determined by EA-IRMS. Most of the compounds were related to the chloropesticides DDT and its metabolites, hexachlorocyclohexanes, and toxaphene, as well as several polybrominated compounds such as bromophenols and -anisoles. δ²H-values ranged between −235‰ and +75‰ whereas δ¹³C-values were found in the range −22‰ to −38‰. No correlation between δ²H- and δ¹³C-values could be identified. Comparative analysis clarified that bromophenols and the corresponding bromoanisoles may vary in their isotopic distribution. ²H NMR was used to quantify abundances of ²H isotopomers. Quantification of isotopomers of 2,4-dibromophenol and 2,4-dibromoanisole proved that both compounds from different suppliers do not originate from the same source. Differences in the δ²H-values of two toxaphene products were further investigated by the synthesis of products of different degree of chlorination from camphene. It was shown that the δ¹³C-values remained mostly unaltered as was expected since no carbon is lost in this procedure. However, the reaction products became enriched in ²H with increasing degree of chlorination. Different δ²H-values of the starting material will also impact the δ²H-values of the chlorination products.     

Rapid and efficient microwave-assisted synthesis of 5-amino-3-aralkoxy(methoxy)amino-1,2,4-oxadiazoles

The microwave-assisted synthesis of 5-amino-3-aralkoxy(methoxy)amino-1,2,4-oxadiazoles starting from N¹-aralkoxy-(methoxy)-N³-cyano-O-phenylisoureas and hydroxylamine is described. N¹-Aralkoxy(methoxy)-N³-cyano-O-phenylisoureas are readily accessible by treatment of diphenyl N-cyanimidocarbonate with O-substituted hydroxylamines.     

Synthesis, cure kinetics, and thermal properties of a novel boron–silicon hybrid polymer

A novel boron–silicon hybrid polymer (PASB) was synthesized from polycondensation between phenylboron dichloride and dichloromethylsilane with Grignard reagent. The structure of PASB was characterized using fourier transform infrared spectra, ¹H-NMR, ¹³C-NMR, and gel permeation chromatography. The curing behavior of PASB was investigated by means of non-isothermal differential scanning calorimetry and the kinetic parameters were determined by the Kissinger’s and Ozawa’s methods, respectively. The results showed that both the methods for calculating the activation energy value gave fairly close results of 104.4 and 107.7 kJ mol^?1, respectively. A reasonable curing cycle for the resin system was also established, which suggested that it was reasonable to choose a curing temperature between T _i0 (452.0 K) and T _f0 (554.0 K). These results can provide theoretical guidance reference for determining the curing of the resin system. The thermal stability of cured PASB resin was studied by means of thermogravimetric analysis under nitrogen atmosphere and the temperature of 5 % mass loss (Td₅) was 610.1 °C, the residue at 1,000 °C was 87.8 %, which showed that the cured PASB resin exhibited excellent thermal properties and made it potentially useful as high performance matrix resin and precursor for ceramics.     

Hydrogenation of CO2 to formic acid in the presence of the Wilkinson complex

Formic acid was synthesized in a high yield at room temperature in the presence of the Wilkinson complex and an excess of PPh₃. The catalytic properties of the rhodium complex depend strongly on the reaction conditions. The mechanism of the rhodium catalyst deactivation was studied by the kinetic method and ³¹P NMR spectroscopy. The methods for the stabilization of the rhodium catalyst were found.     

Mechanistic studies on the formation of Pt(II) hydroformylation catalysts in imidazolium-based ionic liquids

The kinetics of the formation of the active species cis-[Pt^II(PPh₃)₂Cl(SnCl₃)] and cis-[Pt^II(PPh₃)₂(SnCl₃)₂] from the hydroformylation catalyst precursor cis-[Pt^II(PPh₃)₂Cl₂] in the presence of SnCl₂, was studied in two different imidazolium-based ionic liquids. A large range of different chlorostannate melts consisting of 1-butyl-3-methyl-imidazolium cations and [Sn_xCl_y]^{(−y + 2x)} anions with varying molar fraction of SnCl₂, were prepared and characterized by ¹H and ¹¹⁹Sn NMR. The observed chemical shifts point to major changes in the composition of the anionic species within the melt. The second ionic liquid employed, viz., 1-butyl-3-methyl-imidazolium-bis(trifluormethylsulfonyl)amide was prepared in a colorless quality that enabled its application in kinetic studies. The concentration and temperature dependence of the substitution of Cl⁻ by [SnCl₃]⁻ to yield cis-[Pt^II(PPh₃)₂Cl(SnCl₃)], could be studied in detail. Theoretical (DFT) calculations were employed to model the reaction progress and to resolve the role of the ionic liquid in the activation of the catalyst. The available results are presented and a plausible mechanism for the formation of the catalytically active species is suggested.     

Curing of urea-formaldehyde resins on awood substrate

TG-DTA analysis method was used to study the curing behaviour of urea-formaldehyde (UF) adhesive resins in the presence of a wood substrate. The cure process was followed using a Setaram labsys^TM instrument in flowing nitrogen atmosphere by varying the ratio of resin and wood. Resin cure was catalysed with 2% of NH₄Cl. Curing tests were performed in the open standard platinum crucibles and in the sealed glass capsules. To characterise the reactivity of curing system, the peak temperatures in DTA curve and the mass loss values in TG curve were taken as the apparent indices. The main attention was paid to phenomena which actually take place in curing of UF resins during manufacturing of particleboards. Reactivity of the curing system depends mostly on methylol content of resin and can be adequetly evaluated by the maximum temperature of exothermic peak. The wood substrate has a substantial influence on the resin and water diffusion in system causing the changes in water/resin separation and water evaporation conditions. The water movement in curing adhesive joint was a confusing parameter in determining the peak positions. The rate of mass loss on a wood substrate is higher as compared to curing UF resin alone.     

Synthesis of enantiopure β-amino alcohols via AKR/ARO of epoxides using recyclable macrocyclic Cr(III) salen complexes

A series of chiral macrocyclic Cr(III) salen complexes 1-8 were synthesized and characterized. These complexes were found to be highly active, regio-, diastereo-, and enantioselective catalysts in aminolytic kinetic resolution (AKR) of racemic trans-epoxides as well as asymmetric ring opening (ARO) of prochiral meso-epoxides with various anilines as nucleophiles at room temperature in 18-24 h. Excellent yields (>99% with respect to the nucleophile) with high enantioselectivity (ee, >99%) of chiral anti-β-amino alcohols was achieved with concomitant recovery of corresponding epoxides in high ee (up to >99%). The complex 1 also catalyzed the ARO of meso-epoxides to provide corresponding syn-β-amino alcohols in high yield (99%) and ee (up to 91%). Due to built-in basic sites in the catalyst, no external base (as an additive) was required to promote AKR and ARO reactions. The catalyst 1 was conveniently recycled several times with retention of its performance. The AKR of trans-stilbene oxide with aniline was successfully demonstrated at relatively higher scale (10 mmol) using the catalyst 1.     

Quaternized amino functionalized cross-linked polyacrylamide as a new solid-liquid phase transfer catalyst in reduction of carbonyl compounds with NaBH4

Poly[N-(2-aminoethyl)acrylamido]trimethyl ammonium chloride resin was developed as a new polymeric phase transfer catalyst. This quaternized polyacrylamide catalyzed the chemoselective reduction of aldehydes and ketones by NaBH₄ to give corresponding alcohols in high yields under mild conditions.     

Synthesis of cyclic peptides via O-N-acyl migration

We describe here a novel and convenient synthesis of head-to-tail cyclic peptide avoiding racemization. Linear depsipeptides including a serine residue as the key element for ester bond formation and acyl transfer were synthesized on 2-chlorotrityl chloride resin. After cleavage from the resin, intramolecular head-to-tail cyclization was performed in solution by C-terminal activation of urethane protected O-acyl serine residue. After removal of the N^α-serine protecting group, the final step consisted in O-N-acyl migration reaction on the ‘switch’ or ‘click’ element to restore native cyclic peptides.