Characteristics optimization of activated alumina desiccants based on product of a centrifugal thermal activation of gibbsite

Activated alumina desiccants modified with NaOH and KOH were synthesized from the product of a centrifugal thermal activation of gibbsite, with the subsequent hydration in an acid or alkaline medium, and their properties were studied. It was shown that the modification makes it possible to raise the dynamic capacity of desiccants produced from pseudoboehmite by up to a factor of 2 via formation of new super-strong basic centers the concentration of which grows with increasing content of an alkaline oxide. A correlation was found between the total concentration of basic centers on the surface of the desiccants and their dynamic capacity in drying of both dry and humid air. Use of the modified desiccants with high static and dynamic capacity will make it possible to improve the drying efficiency.     

Effect of modifying alumina desiccants with sulfuric acid on their physicochemical properties

In the production of alumina desiccants by extrusion, the introduction of sulfuric acid at the stage of preparing a mouldable paste based on hydroxides containing bayerite or pseudoboehmite increases the sorption capacity of the product. This effect is most pronounced for the pseudoboehmite-based materials. The dynamic capacity of these desiccants increases to the level characteristic of the bayerite-containing hydroxide (>5 g H₂O/100 cm³) for a dew point of ?40°C and a contact time of 1.5 s), and their static capacity exceeds this value (increasing from 21.13 to 23.1 g H₂O/100 cm³). This procedure changes the phase composition and textural characteristics of the pseudoboehmite-based desiccants and increases Brønsted acidity and generates strong Lewis acid sites on the surface of all oxides. The dynamic capacity of desiccants with similar textural characteristics depends on the acid-base properties of their surface.     

Morphological Stability of the Solid–Liquid Interface during Melt Crystallization of Ca1–xSrxF2 Solid Solution

Crystallography Reports - Proceeding from the phase diagram of the CaF2–SrF2 system, the stability of crystal–melt interface of solid solution against constitutional supercooling has...     

Dioximes of 1,6-heptanediones from acetylene and ketones: only three atom-economic steps

1. Download high-res image (92KB)
2. Download full-size image

     

Variable temperature NMR and theoretical study of the stereodynamics of 5-trifluoromethylsulfonyl-1,3,5-dioxaazinane: Perlin effect subject to heteroatom substitution

Multinuclear dynamic NMR spectroscopy of 5-trifluoromethylsulfonyl-1,3,5-dioxaazinane (4) revealed the existence of two close in energy chair conformers with differently oriented CF₃ groups with respect to the ring. Of the two alternative routes for their interconversion, the ring inversion path with intermediate formation of the corresponding 2,5-twist-conformer is preferred, with the energy barrier of 11.2 kcal/mol in excellent agreement with the experimental value (11.7 kcal/mol). The Perlin effect is studied experimentally and calculated theoretically for all CH₂ groups and found to be subject to the nature of the adjacent heteroatoms O and N, respectively.     

Chemo- and regioselective ethynylation of 4,5,6,7-tetrahydroindoles with ethyl 3-halo-2-propynoates

4,5,6,7-Tetrahydroindoles undergo a rapid, facile (rt, 60 min) ethynylation with ethyl 3-halo-2-propynoates upon grinding with solid K₂CO₃ (without solvent) at C-2 of the tetrahydroindole ring to afford ethyl 3-(4,5,6,7-tetrahydroindol-2-yl)-2-propynoates in 62–90% yield.     

Oxymethylation of trifluoromethanesulfonamide with paraformaldehyde in ethyl acetate

Acid-catalyzed reaction of trifluoromethanesulfonamide with paraformaldehyde in ethyl acetate led to the formation of oxymethylated products that did not form in the reaction carried out in sulfuric acid. Following products were obtained: 5-trifluoromethylsulfonyl-1,3-dioxazinane, 3,7-bis-(trifluoromethylsulfonyl)-1,5,3,7-dioxadiazocane, and a complex of trifluoromethanesulfonamide with 2,4,8,10-tetraoxospiro[5,5]undecene, 1:1. The spiroring resulted from the cyclization of pentaerythritol under the action of formaldehyde. The pentaerythritol formed in its turn by oxymethylation of the methyl group of ethyl acetate with paraformaldehyde followed by the reduction of the COOEt group into CH₂ OH by the formaldehyde.     

Comparative analysis of hydrogen bonding with participation of the nitrogen, oxygen and sulfur atoms in the 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives based on the 1H, 13C, 15N spectroscopy and DFT calculations

The N-H...X (X = N,O,S) intramolecular hydrogen bond in the series of 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives is examined by the (1)H, (13)C, (15)N spectroscopy and density functional theory (DFT) calculations. The influence of the hydrogen bond on coupling and shielding constants is considered. It is shown that the N-H...N intramolecular hydrogen bond causes a larger increase in the absolute size of the (1)J(N,H) coupling constant and a larger deshielding of the bridge proton than the N-H...O hydrogen bond. The effect of the N-H...S interaction on the (1)J(N,H) coupling constant and the shielding of the bridge proton is small. The NMR parameter changes in the series of the 2(2'-heteroaryl)pyrroles due to N-H...X hydrogen bond and the series of the 1-vinyl-2-(2'-heteroaryl)-pyrroles due to C-H...X hydrogen bond have the same order. The proximity of the nitrogen, oxygen or sulfur lone pair to the F...H hydrogen bridge quenches the trans-hydrogen bond spin-spin couplings (1h)J(F,H-1) and (2h)J(F,N).     

A guidance problem for a differential inclusion with parameter

A differential inclusion with parameter on a finite time interval is studied. Questions related to determining the solvability set in the problem of guiding a differential inclusion to a compact target set in the phase space are discussed.