Chalcogenation of 1,3-dichloropropene with elemental chalcogens in the system hydrazine hydrate–base

Sulfur reacts with 1,3-dichloropropene in the system hydrazine hydrate–KOH to form bis(1-chloroprop-1-en-3-yl) sulfide, and in the system hydrazine hydrate–monoethanolamine, bis(1-chloroprop-1-en- 3-yl) disulfide. The reaction of tellurium in the system hydrazine hydrate–KOH leads to diallyl telluride, the product of nucleophilic substitution of the allylic chlorine atom and reductive cleavage of the С_sp2–Cl bond. The reaction of selenium with 1,3-dichloropropene gives a complex mixture of products. At excess KOH (Se: KOH = 1: 5) bis(1-chloroprop-1-en-3-yl) selenide was isolated.     

Synthesis of polydentate chalcogen-containing ligands using the system hydrazine hydrate–base

The reaction of dichlorodiethyl ether or dichlorodiethylamine hydrochloride with potassium or ethanolammonium dichalcogenides prepared in situ from elemental sulfur or selenium in the system hydrazine hydrate–alkali results in oligomeric dichalcogenides, whose further splitting at the chalcogen–chalcogen bond in the same system and subsequent alkylation affords bis(organylsulfanyl)- or bis(organylselanyl)-substituted derivatives of diethyl ether or diethylamine. Ligands with aryl substituents at the chalcogens have been prepared in 48-59% yield by splitting of diaryldichalcogenides in the system hydrazine hydrate–alkali and subsequent reaction with dichlorodiethyl ether or dichlorodiethylamine. A ditopic tetradentate ligand has been synthesized by the use of dichlorodiethylformal.     

Reactions of β,β′-dichlorodiethyl ether with elemental chalcogens and dimethyl dichalcogenides in the system hydrazine hydrate-base

β,β′-Dichlorodiethyl ether reacted with elemental selenium or tellurium, as well as with binary chalcogen mixtures (S/Se, S/Te, or Se/Te), activated in the system hydrazine hydrate-base to give oligomeric products containing oxygen and polychalcogenide fragments in the chain. Reductive cleavage of these oligomers gave rise to 3-oxapentane-1,5-dichalcogenols and their methyl derivatives. The latter were also synthesized from β,β′-dichlorodiethyl ether and the corresponding dimethyl dichalcogenides in the system hydrazine hydrate-KOH.     

Condensation of СН-acids with cis-1,4-dichlorobut-2-ene

Russian Journal of General Chemistry - Synthesis of tri- and five-membered carboxylates are discussed. Microwave irradiation has been shown to stimulate the condensation of СН-acids...     

Reactions of α-perfluorophenylpyrylium perchlorates with hydrazine hydrate

Reactions of α-perfluorophenylpyrylium salts with hydrazine hydrate in ethanol afforded derivatives of 1,2-diazepine, dihydro-1H-pyrazole, and/or 1-aminopyridinium salts, depending on the steric characteristics of the substituent in the second α-position. 1-Amino-2-methyl-6-perfluorophenyl-4-phenylpyridinium perchlorate was used to obtain various pyridocyanines.     

Formation of 2-methyl-3,5-diphenylfuran from chalcone and acetylene in the system KOH–DMSO

Russian Journal of Organic Chemistry - Chalcone reacted with acetylene in a suspension of KOH in DMSO at 90°C (30 min) to give 36% of 2-methyl-3,5-diphenylfuran.     

Test of the water adsorption model of organic electrocatalysis in the carbon monoxide–silver system in alkaline medium

A test has been carried out of the model of T. Iwasita, X.H. Xia, H.-D. Liess, W. Vielstich [J. Phys. Chem. B. 101 (1997) 7542], according to which the maximum at about the same potential in both the positive and negative sweeps in cyclic voltammograms (CVs) of small organic molecules on Pt is due to the concurrence of two processes with opposite potential dependences, adsorption of the organic compound and electrooxidation of its intermediates, which decrease and increase, respectively, with increasing potential. In turn, the decrease with increasing potential of the adsorption of the undissociated organic is due to its increasing displacement by molecular water, this competition occurring because the two molecular compounds have similar, low values of the adsorption energy. According to the model of T. Iwasita, X.H. Xia, H.-D. Liess, W. Vielstich [J. Phys. Chem. B. 101 (1997) 7542], with CO on Pt no anodic currents are observed in the negative sweep because of the high adsorption energy of CO on Pt, which precludes its displacement by water. Therefore, the model has been tested with the CO–Ag system, for which anodic currents should be observed in the negative sweep, since the adsorption energy of CO on Ag is very low. Effectively, this has been found to be the case, which indicates that the model is indeed applicable to the CO–Ag system over the tested pH range, 10–14. At pH⩽11 adsorbed CO was displaced from the surface of Ag by N₂ bubbling, while it was not at pH⩾12. However, even at pH⩾12 the adsorption energy of CO on Ag should be rather weak, since anodic currents appeared in the negative sweep in CO-saturated solution over the whole pH range tested, 10–14.     

Individual extraction constants of some organic cations in the two-phase water–nitrobenzene system

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium C⁺(aq) + Cs⁺(nb) ⇔ C⁺(nb) + Cs⁺(aq) taking part in the two-phase water–nitrobenzene system (C⁺ = organic cation; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the individual extraction constants of 15 organic cations in the mentioned two-phase system were calculated.     

Determination partition coefficients of volatile organic substances in the system liquid–air for the creation of calibration gas-phase samples with trace concentrations of substances

The results of determination of Henry’s coefficients for an equilibrium vapor containing trace concentrations of acetone, benzene, toluene, and xylenes over their aqueous solutions are presented. Continuous gas extraction is used.     

Formation of 1-aminophenazine from 3,4-dihydrophenazin-1(2H)-one oxime in the system acetylene–KOH–DMSO

Russian Journal of Organic Chemistry - The reaction of 3,4-dihydrophenazin-1(2H)-one oxime with acetylene in the superbasic system KOH–DMSO afforded 1-aminophenazine in 32% yield instead of...     

Reaction of 2-methylquinoline with 3-phenylprop-2-ynenitrile in the KOH—H<Subscript>2</Subscript>O system

The reaction of 2-methylquinoline with 3-phenylprop-2-ynenitrile in the presence of water (0—25 °C, 20 mol.% KOH, 5 equiv. H₂O) is accompanied by the loss of aromaticity of the quinoline nucleus and results in double functionalization of the molecule at the nitrogen atom and the methyl group. Two 2-cyano-1-phenylethenyl groups were introduced into the molecule to form (2E,4E)-4-{1-[(Z)-2-cyano-1-phenylethenyl]quinolin-2(1H)-ylidene}-3-phenylbut-2-enenitrile in 59—67% yield. This reaction is stereoselective: the N-2-cyano-1-phenylethenyl-substituent has the Z-configuration, while the 1,3-diene moiety at the methyl group has the E,E-configuration. (2E)-3-Phenyl-4-(quinolin-2-yl)but-2-enenitrile that formed as a by-product (0—24% yields) is formally the addition product of the methyl group of the quinoline substrate at the acetylenic bond.     

Reactivity of α-Amino Acids in the Reaction with Esters in Aqueous–1,4-Dioxane Media

The kinetics of the reaction of a series of α-amino acids with 4-nitrophenyl acetate, 4-nitrophenyl benzoate, and 2,4,6-trinitrophenyl benzoate in aqueous 1,4-dioxane medium has been studied. Kinetics of the reactions involving 4-nitrophenyl acetate and 2,4,6-trinitrophenyl benzoate has complied with the Brønsted dependence and revealed linear correlation between rate constant logarithm and the energy difference of the frontier orbitals of α-amino acids anions.     

Gas hydrate formation in the system C2H6–H2–H2O at pressures up to 250 MPa

Decomposition curves of gas hydrates formed in the ethane–hydrogen–water system were studied in the pressure interval 2–250 MPa. Gas hydrates synthesized at low (up to 5 MPa) pressures were also studied with use of X-ray powder diffraction and Raman spectroscopy. It was shown that ethane–hydrogen mixtures with hydrogen contents 0–30 mol.% form cubic structure I gas hydrates. Higher hydrogen concentration most probably results in appearance of another hydrate phase. We speculate that the gas mixtures with the hydrogen content above 60 mol.% form cubic structure II double hydrate of hydrogen and ethane at temperatures below ≈280 K and pressures above 25 MPa.     

Improvement of the bioactivity of organic–inorganic hybrid aerogels/wollastonite composites with TiO2

Organic–inorganic hybrid aerogels containing P and Ti have been synthesized by supercritical drying of alkogels prepared by hydrolysis and poly-condensation of metalo-organic precursors under high-power ultrasound. These materials become bioactive when doped with Ca. Wollastonite particles (CaSiO₃) were added as an active phase, instead of incorporating Ca into the aerogel atomic network. These particles had previously been precipitated and were then added to the sol. The aerogels were studied by Fourier transform infrared analysis, scanning electron microscopy coupled with energy dispersive spectroscopy and X-ray diffraction and N₂ adsorption. The stress–strain behaviours were evaluated under compression to obtain the Young’s modulus. It was found that the incorporation of TiO₂ into wollastonite-P₂O₅ hybrid aerogels increased their capacity to form apatite and, consequently, improving their bioactive response.     

An experimental study of the stability of TiO2 particles in organic–water mixtures

The stability of TiO₂ (Anatase) particles in various organic-water mixtures is examined experimentally. The results obtained reveal that the addition of AlCl₃ to a methanol–water dispersion leads to charge reversal on particle surface. If the concentration of methanol is high, CaCl₂ also leads to charge reversal, but NaCl does not have this effect. This implies that if the concentration of methanol is low, the coagulation between TiO₂ particles is due to double-layer compression for Na⁺ and Ca²⁺, and due to charge adsorption and neutralization for Al³⁺. A methanol dispersion is unstable without the addition of electrolyte, and the addition of both CaCl₂ and AlCl₃ has the effect of stabilizing the dispersion; the addition of NaCl does not have this effect. The qualitative behaviors of an acetone–water dispersion are similar to those of a methanol–water dispersion. It is interesting to observe, however, that the absolute mobility of a pure acetone dispersion has a maximum as the concentrations of both CaCl₂ and AlCl₃ vary, but charge reversal does not occur. Among the dispersions without the addition of electrolyte, a 50% organic–water mixture is most stable. Also, a methanol–water dispersion is more stable than an acetone–water dispersion, which can be explained based on the degree of dissociation of an electrolyte.     

Interactions of CO2 with cluster models of metal–organic frameworks

The interactions between carbon dioxide and cluster models of coordinatively unsaturated metal–organic frameworks (MOFs) were studied using a variety of ab initio methods. Three metal species and three organic linkers in four structures were considered in these models as a representation of the tunable nature of MOFs and the potential multireference character of such systems. Common single-reference methods, such as MP2 and CCSD(T), were compared with multireference methods based on complete active space self-consistent field theory, going as far as multireference configuration interaction with single and double excitations (MRCISD). Special consideration is taken to avoid issues of size inconsistency in the CI results, where an alternate reference is used in the interaction energy definition. The benchmark values are used to judge the adequacy of a selection of density functionals for the current systems. Symmetry-adapted perturbation theory (SAPT) decomposition was performed to elucidate the important effects that comprise the binding interactions. The systems proved to have very limited multireference character, and MP2 values were closer to the CCSD(T) benchmark than the more difficult MRCISD results. Though the SAPT total energies prove to be relatively poor approximations to the benchmark interaction energies, they reveal (in most cases) the correct trends with respect to the choice of the metal. The SAPT energy decompositions indicate that the CO₂ binding is primarily driven by electrostatics, but induction and dispersion also provide sizable, and quite similar, attractive contributions. Importantly, the small diformate model provides a faithful representation of complexes with large aromatic linkers, both in terms of the total interaction energy and the SAPT decomposition.