Showing papers in "Russian Chemical Bulletin in 1985"
TL;DR: The effect of polyhydroxynaphthoquinones on the low-temperature oxidation of cumene was investigated in this article, where the rate constants for reaction with the peroxy radical were comparable to or greater than that for 2,6-di-tert-butyl-4-methylphenol.
Abstract: 1.
The effect of natural polyhydroxynaphthoquinones on the low-temperature oxidation of cumene was investigated. These compounds constitute a new class of antioxidants, the rate constants of which for reaction with the peroxy radical are comparable to or greater than that for 2,6-di-tert-butyl-4-methylphenol.
2.
2,3,5,7,8-Pentahydroxy-6-ethylnaphthalene-1,4-dione is the most effective of the investigated antioxidants.
20 citations
TL;DR: The hydrolysis of alkyladamantanol nitrates by dilute nitric acid gives the corresponding alkyl-adamantanols as mentioned in this paper, which are formed by the treatment of corresponding alklamantanes with fuming nitric acids.
Abstract: 1.
Alkyladamantanol nitrates are formed by the treatment of the corresponding alkyl-adamantanes with fuming nitric acid.
2.
The hydrolysis of alkyladamantanol nitrates by dilute nitric acid gives the corresponding alkyladamantanols.
17 citations
TL;DR: In this paper, a mechanism was established for the reaction of 4-X-3,6-di-tert-butyl-o-benzoquinone (X=H, Cl) with SO 2Cl2 involving the protonation of SO2Cl2.
Abstract: 1.
A study of the chlorination of 3,6-di-tert-butylpyrocatechol and its corresponding quinone and 4-chloro-3,6-di-tert-butyl-o-benzoquinone by sulfuryl chloride showed that this method may serve as a preparative method for obtaining 4-chloro-3,6-di-tert-butyl-o-benzoquinone and 4,5-dichloro-3,6-di-tert-butyl-o-benzoquinone.
2.
A mechanism was established for the reaction of 4-X-3,6-di-tert-butyl-o-benzoquinone (X=H, Cl) with SO2Cl2 involving the protonation of SO2Cl2.
15 citations
TL;DR: Functional derivatives of alkyladamantanes may also be obtained in good yields from the corresponding alkylamantanol nitrates as mentioned in this paper, where the derivatives are derived from a mixture of alkaline alkyl compounds.
Abstract: Functional derivatives of alkyladamantanes may be obtained in good yields from the corresponding alkyladamantanol nitrates.
14 citations
TL;DR: In this article, a method was developed for the preparation of N-alkyl-N-nitroso-hydroxylamine salts by treating alkylmagnesium halides with nitric oxide, yields of 40-60% being obtained.
Abstract: 1.
A method has been developed for the preparation of N-alkyl-N-nitrosohydroxylamine salts by treating alkylmagnesium halides with nitric oxide, yields of 40–60% being obtained. The reaction of chloromagnesium or potassium salts of N-alkyl-N-nitrosohydroxylamines with dimethyl sulfate has afforded 20–30% of N-alkyl-N′-methoxydiazene N-oxides, calculated on the alkylmagnesium halide taken.
2.
According to their IR spectra, p-π conjugation is present in N-alkyl-N′-methoxydiazene N-oxides.
13 citations
TL;DR: A dicationic organogold ferrocenyl complex containing four gold atoms was obtained by the action of triphenylphosphine gold tetrafluoroborate on 1,1′-bis(triphenyl phosphine gold)ferrocene as discussed by the authors.
Abstract: 1.
A dicationic organogold ferrocenyl complex containing four gold atoms, namely {[(Ph3PAu)2C5H4]2Fe}++(BF4−)2, was obtained by the action of triphenylphosphinegold tetrafluoroborate on 1,1′-bis(triphenylphosphinegold)ferrocene.
2.
The reaction of 1,1′-ferrocenyl-bis(triphenylphosphinegold) with HBF4 leads to cleavage of one C-Au bond and the formation of a binuclear cationic complex, namely, [C5H5 FeC5H4,(AuPPh3)2]+BF4−.
10 citations
TL;DR: In this article, the adsorption of methane on NaX zeolite in the subcritical and supercritical regions was studied, and it was found that the adorption isoteres are linear in the range of pressures from ∼0.1 Pa to ∼20 MPa and temperatures from 120 to 600°K.
Abstract: 1.
The adsorption of methane on NaX zeolite in the subcritical and supercritical regions was studied, and it was found that the adsorption isoteres are linear in the range of pressures from ∼0.1 Pa to ∼20 MPa and in the range of temperatures from 120 to 600°K. The adsorption isosteres, interrupted at the methane saturated vapor pressure line, subsequently continue linearly in the supercritical region.
2.
The first adsorbed molecules at relatively low temperatures are adsorbed in deep potential wells, which naturally realizes the Langmuir model of adsorption in zeolite.
10 citations
TL;DR: The previously unknown 9-vinyl- and 9-ethynyl-o-and m-carboranes were obtained by the reaction of vinyl- and ethynylmagnesium halides with 9-iodo-o-, 9-Io-m-carbors, catalyzed by palladium complexes as mentioned in this paper.
Abstract: The previously unknown 9-vinyl- and 9-ethynyl-o- and m-carboranes were obtained by the reaction of vinyl- and ethynylmagnesium halides with 9-iodo-o- and 9-iodo-m-carboranes, catalyzed by palladium complexes
10 citations
TL;DR: In this article, a 4,4-Difluoroacetoacetic ester with ethylenediamine yields the 3,3′-(N,N′-ethylenediamines)-bis-4, 4-difluor-2-butenoate ester whereas on lengthening the fluoroalkyl substituent internal salts of the aminoethylamides of the β-keto acids are formed from the β -ketoesters.
Abstract: 1.
Fluoroalkyl β-ketoesters with phenylhydrazine at 20‡C form phenylhydrazones of the β-ketoesters, which form hydroxypyrazoles on heating.
2.
4,4-Difluoroacetoacetic ester with ethylenediamine yields the 3,3′-(N,N′-ethylenediamine)-bis-4,4-difluoro-2-butenoate ester whereas on lengthening the fluoroalkyl substituent internal salts of the aminoethylamides of the β-keto acids are formed from the β-ketoesters.
3.
Hydrazine and o-phenylenediamine react with fluorine-containing β-ketoesters with the formation of pyrazoles and benzodiazepinones respectively.
9 citations
TL;DR: The thermal stability of ZSM-5 zeolites increases as the Na content of the crystals is reduced and can be appreciably increased by chemical modification, which leads to decation of the crystal as mentioned in this paper.
Abstract: 1.
The likelihood of obtaining silicalites 1 or 2, distinguished by the structural features of their framework, depends on the composition of the mixtures used in their preparation. The nature of the organic component has the greatest influence on the results of the crystallization. Complete absence of sodium ions from the mixture used in the synthesis of silicalite 2 is not obligatory.
2.
Under certain conditions of synthesis silicalites are obtained whose diffractograms seem to indicate a combination of the structural features of both silicalites 1 and 2 in the framework.
3.
Considerable differences in the thermal stability of silicalite samples are determined by the Na content. The thermal stability of silicalites, as of ZSM-5 zeolites, increases as the Na content of the crystals is reduced and can be appreciably increased by chemical modification, which leads to decationation of the crystals.
8 citations
TL;DR: In this article, the magnetic resonance data in the 3 cm and 2mm ESR bands with the electrical indices of compounds containing polythiophene (PT) and polyacetylene (PA).
Abstract: This paper compares the magnetic resonance data in the 3-cm and 2-mm ESR bands with the electrical indices of compounds containing polythiophene (PT) and polyacetylene (PA). ESR signals were not found for PT combined with FeC1/sup -//sub 4/, and MnO/sup -//sub 4/ anions. A dependence of the magnetic resonance parameters on the nature of the anion was established for organic polythiophene conductors with various anions. The major values of the anisotropic g-tensor were measured by 2-mm band spectroscopy and the conductivity of polythiophene (BF/sup -//sub 4/) and polyacetylene (I/sup -/) was evaluated at 200 K.
TL;DR: In this paper, the intermediate formation of vanadium(5+) peroxo complexes was detected under conditions of the disproportionation of hydrogen peroxide in acetic acid catalyzed by ammonium metavanadate by51V NMR spectroscopy.
Abstract: The intermediate formation of vanadium(5+) peroxo complexes was detected under conditions of the disproportionation of hydrogen peroxide in acetic acid catalyzed by ammonium metavanadate by51V NMR spectroscopy and the complex of vanadium(5+) ions with the dioxygen radical-anion was detected by ESR spectroscopy.
TL;DR: In this paper, a cross combination reaction of aryl iodides with trifluorovinylzinc chloride catalyzed by palladium complexes was used to obtain trifloorostyrene and its derivatives.
Abstract: A method of obtaining trifluorostyrene and its derivatives (p-Me, p-MeO, p-Cl) has been developed by the cross combination reaction of aryl iodides with trifluorovinylzinc chloride catalyzed by palladium complexes. In the case of aryl iodides with strong electron accepting substitutents a stable palladium complex was formed which did not react in the cross combination reaction. Under more drastic conditions it is possible to use trifluorovinyltrialkylstannanes in place of the organozinc compounds.
TL;DR: X-ray diffraction study of (Et2O)2·HZnCl3 showed that its crystal consists of centrosymmetric [ZnCL6]2− dianions and [Et 2OOEtp2]+ cations, without close contacts between them.
Abstract: 1
HMCln Friedel-Crafts acids (where M is Al, Zn, Ge, Sn, etc) form (Et2O)2·HMCln etherates with diethyl ether By their IR and1H and13C NMR spectra and x-ray diffraction patterns, these are compounds of similar structure with a short H bond in the cation
2
X-ray diffraction study of (Et2O)2·HZnCl3 established that its crystal consists of centrosymmetric [ZnCl6]2− dianions and [Et2OOEt2]+ cations, without close contacts between them The symmetrical OO segment in the cation has an OO distance of 2394(4) A, which is one of the shortest for this type of H bond
TL;DR: In this paper, the authors show that increasing the time of exposure of aluminum to the sodium oleate solution leads to the formation of polylayers of aluminum oleates on its surface, tightly bonded to the substrate.
Abstract: 1.
The adsorption of sodium oleate on an oxidized aluminum surface is of an irreversible chemical type and decreases the work function by 0.05–0.06 eV. In the complex formed on the surface, the axis of the carboxyl group is oriented perpendicular to the surface.
2.
Increasing the time of exposure of aluminum to the sodium oleate solution leads to the formation of polylayers of aluminum oleate on its surface, tightly bonded to the substrate. In this case the work function decreases by an additional 0.10–0.13 eV, while the orientation of the carboxyl groups is disrupted.
3.
After the exposure of aluminum to concentrated nitric acid, a layer consisting of oxides, nitrogen-containing salts, and aluminum hydroxides is formed on its surface.
4.
Modification of the surface acclerates the chemisorption of sodium oleate and the ion-exchange reaction in solution. In this case the chemisorption of sodium oleate increases the work function by 0.3 eV, while the formation of phase layers of aluminum oleate decreases it by 0.25 eV. In the case of analogous exposures in solution, the thickness of the aluminum oleate layers formed is greater on a modified surface.
TL;DR: In this paper, the Nα-ferrocenylalkylation of the benzotriazolide ion by α-hydroxyferrocensyl derivatives was carried out in a two-phase system consisting of CH2Cl2 and 45% aqueous HBF4 to give high yields of N-ferricenyl-alkylbenzotrieazoles.
Abstract: The N-α-ferrocenylalkylation of the benzotriazolide ion by α-hydroxyferrocenyl derivatives was carried out in a two-phase system consisting of CH2Cl2 and 45% aqueous HBF4 to give high yields of N-ferrocenylalkylbenzotriazoles.
TL;DR: In this paper, a regioselective method was developed for the carbometallation of higher α-olefins using Et3Al and Et2AlCl in the presence of titanium and zirconium complexes which permits the preparation of higher trialkylaluminums and dialkylaluminum halides in high yield under mild conditions in one step.
Abstract: A regioselective method was developed for the carbometallation of higherα-olefins using Et3Al and Et2AlCl in the presence of titanium and zirconium complexes which permits the preparation of higher trialkylaluminums and dialkylaluminum halides in high yield under mild conditions in one step.
TL;DR: In this paper, the hydrazides of vicinal phenylethynyl derivatives of N-methylpyrazole-5-carbo-xylic and benzoic acids are respectively cyclized into 6,7-dihydro-6-amino-1-methyl-5phenylpyrido[3,4-c]pyrazol-7-one and 2-amide-3-benzylideneisoindolin-1,one under the effect of bases.
Abstract: 1.
The hydrazides of vicinal phenylethynyl derivatives of N-methylpyrazole-5-carbo-xylic and benzoic acids are respectively cyclized into 6,7-dihydro-6-amino-1-methyl-5-phenylpyrido[3,4-c]pyrazol-7-one and 2-amino-3-benzylideneisoindolin-1-one under the effect of bases.
2.
The hydrazide of 4-phenylethynyl-1-methylpyrazole-5-carboxylic acid and the cyclic isomer of tolan-2-carboxylic acid hydrazide, 2-amino-3-benzylideneisoindolin-1-one, are isoraerized in the presence of CuCl with closure of the six-membered pyridazine ring.
3.
6,7-Dihydro-6-amino-1-methyl-5-phenylpyrido[3,4-c]pyrazol-7-one and 2-amino-3-benzylideneisoindolin-1-one are deaminated in oxidation with air in the presence of CuCl.
TL;DR: In this paper, a comparative study of the thermal stability of ZSM-5 zeolites prepared under different conditions and with different compositions was carried out, where the level of thermal stability was evaluated in terms of the point of intersection of the curve with the dashed line presented in a graph.
Abstract: The authors have carried out a comparative study of the thermal stability of ZSM-5 zeolites prepared under different conditions and with different compositions. Zeolites were prepared at 150 C in an aluminate-silicate system. Diffractograms indicate that both after removal of the organic component on heating and after chemical modification, the structure of the zeolite framework was retained. The level of thermal stability was evaluated in terms of the point of intersection of the curve with the dashed line presented in a graph. Data from differential thermal analysis, obtained with dynamic heating on a DTA instrument at 10 C/min. were also employed in the evaluation of thermal stability.
TL;DR: The enthalpies of dissolution of guanidinium perchlorate and chloride have been measured, and the standard enthalpy of their formation have been calculated: ΔHf,298.150 [C(NH2)3ClO4]c=−74.35 ± 0.21 kcal/mole as discussed by the authors.
Abstract: 1.
The enthalpies of combustion and dissolution of guanidinium nitrate have been measured. The standard enthalpy of formation of guanidinium nitrate has been calculated: ΔHf,298.150[C(NH2)3NO3]c=−92.47±0.17 kcal/mole.
2.
The enthalpy of formation of the guanidinium ion in infinitely dilute aqueous solution has been calculated: ΔHf,298.150[C(NH2)3+(∞H2O=−33.24±0.21 kcal/mole].
3.
The enthalpies of dissolution of guanidinium perchlorate and chloride have been measured, and the standard enthalpies of their formation have been calculated:ΔHf,298.150 [C(NH2)3ClO4]c=−74.35 ± 0.22 kcal/mole;ΔHf,298.150 [C(NH2)3Cl]c=−77.66±0.21 kcal/mole.
TL;DR: In this article, the path length before localization of a photoliberated electron increases with increasing mobility of the excess electron, from approximately 40 A (methylcyclohexane) to 200 A (isooctane) in liquid hydrocarbons.
Abstract: On the basis of measurements of values ofμ′τ′ in liquid hydrocarbons, it has been shown that the path length before localization of a photoliberated electron increases with increasing mobilityμ of the excess electron, from approximately 40 A (methylcyclohexane) to 200 A (isooctane) In a liquid withμ10−2 cm2/V·sec (methylcyclohexane, hexane), the localization takes place before or immediately after thermalization of the electron In a liquid withμ>10−1 cm2/V·sec, the electron passes through the main part of its path before localization, being in thermal equilibrium with the medium
TL;DR: In this article, a method has been developed for obtaining hydroborate complexes of copper with various organophosphorus ligands (tertiary and secondary phosphines, tertiary phosphites, phosphonites, amidophosphites) by the action of ionic hydroborates on the corresponding copper complexes.
Abstract: 1.
A method has been developed for obtaining hydroborate complexes of copper with various organophosphorus ligands (tertiary and secondary phosphines, tertiary phosphites, phosphonites, amidophosphites) by the action of ionic hydroborates on the corresponding copper complexes in aprotic solvents. The IR absorption spectra of the obtained complexes have been measured.
2.
The influence of the electronic and steric properties of the organophosphorus ligands on the composition and structure of the hydroborate complexes of copper has been considered. It was shown that an increase in electron-donating properties and a reduction in the volume of the organophosphorus ligand promoted the formation of complexes with a monodentate hydroborate group.
3.
The crystal and molecular structure of Cu(PBuPh2)2(BH4), a compound with a bidentate hydroborate group, has been determined.
TL;DR: In this paper, the ability of methyl esters of 1-alkylcyclopropene-3-carboxylic acids to cyclopropanate norbornadiene or dicyclopentadiene, with the formation in up to 75% yield of the corresponding vinylcyclopropane adducts has been discovered.
Abstract: 1.
The ability of methyl esters of 1-alkylcyclopropene-3-carboxylic acids to cyclopropanate norbornadiene or dicyclopentadiene, in the presence of copper (I) chloride or its complexes, with the formation in up to 75% yield of the corresponding vinylcyclopropane adducts has been discovered. Products were the methyl esters of 3-(tricyclo[3. 2.1.02,4]oct-6-en-3-yl)alk-2-enoic and 3-(tetracyclo[5.3.1.02,608,10]undec-3-en-9-yl)alk-2-enoic acids respectively.
2.
The methyl esters of 1-alkylcyclopropenecarboxylic acids were isomerized, in a medium of cycloocta-1,5-diene, cyclohexene, methylenecyclopropane, or methyl acrylate in the presence of copper (I) chloride or its complexes, into 2-methoxy-4-alkylfuran (yields up to 65%) and partially oligomerized, but with cyclopentadiene the corresponding diene adduct was formed.
3.
A concerted mechanism has been proposed and theoretically substantiated for the formation of vinylcyclopropane derivatives from substituted cyclopropenes and olefins in the coordination sphere of copper without the participation of vinylcarbenes or their complexes.
TL;DR: In this article, the trimerization of phenylacetylene was studied in an alcoholic medium with rhodium and bis(ethylbenzene)molybdenum and nonacarbonylnitrosylhydrideditungsten catalyzes.
Abstract: Hydroxyquinoline complexes of rhodium in an alcoholic medium, as well as bis(ethylbenzene)molybdenum and nonacarbonylnitrosylhydrideditungsten catalyze the trimerization of phenylacetylene.
TL;DR: The azacycloalkanes HNCH2(CH2)nCH2CH2 (n=1−3), on treatment with the Na2S2O8-NaCN-NaOH system, undergo the competing reactions of N-cyanation to give the ureas, C-Cyanation and β-fragmentation to give 2-cyanoazacycloencane, and N
Abstract: 1.
The azacycloalkanes HNCH2(CH2)nCH2CH2 (n=1–3), on treatment with the Na2S2O8-NaCN-NaOH system, undergo the competing reactions of N-cyanation to give the ureas, C-cyanation to give 2-cyanoazacycloalkanes, and β-fragmentation to give N-cyanomethyl- and N-formylazacycloalkanes. The relative proportions of these three competing reactions depend on the size of the ring.
2.
Oxidative β-fragmentation of azacycloalkanes also occurs in the K3Fe(CN)6-NaOH and Na2S2O8-AgNO3-NaOH systems.
TL;DR: In the presence of amines containing α-hydrogen atoms o-quinones are photoreduced to pyrocatechols or monoethers as discussed by the authors, and the rate of photoreduction is inversely proportional to the dielectric constant of the solvent.
Abstract: 1.
In the presence of amines containing α-hydrogen atoms o-quinones are photoreduced to pyrocatechols or monoethers.
2.
The rate of the photoreduction reaction increases as the electron-donating ability of the amine or the electron-withdrawing ability of the quinone is increased; the rate of photoreduction is inversely proportional to the dielectric constant of the solvent.
3.
The photoreduction of o-quinones in the presence of amines occurs via the excited triplet states of the o-quinones according to the generally accepted mechanism for the photoreduction of carbonyl-containing compounds.
TL;DR: In the presence of palladium(0) complexes, quadricyclone is converted to norbornadiene dimers and trimers as discussed by the authors, where the latter is used for trimers.
Abstract: In the presence of palladium(0) complexes, quadricyclone is converted to norbornadiene dimers and trimers.
TL;DR: In this article, the auration of 1,1-ferrocenylenedithiol (II) by tris(triphenylphosphinegold)oxonium tetrafluoroborate was carried out in an argon atmosphere.
Abstract: In a continuation of a study of the reactions of aurous complex salts with ferrocene thio derivatives, the authors studied the auration of 1,1-ferrocenylenedithiol (II). The auration of dithiol (II) by tris(triphenylphosphinegold)oxonium tetrafluoroborate was carried out in an argon atmosphere. Relative to the auration of ethyl cyanoacetate, the aurating capacity of the tris-(triphenylphosphinegold)sulfonium tetrafluorobroate is significantly lower than that of (Dh/sub 3/PAu)/sub 3/>0 +BF-/sub 4/ and (Ph/sub 3/PAu)/sub 4/N /SUP BF/ >-/sub 4/.
TL;DR: In this paper, the selectivity decreases upon the addition of acetone to all the alcohols studied and the dilution of the alcohol by acetone does not affect the yields of the carbonylation of 1-nonene in 1-propanol but causes a decrease in this yield in 1butanol and 1-heptanol.
Abstract: 1.
The yields of the products of the carbonylation of 1-nonene in normal alcohols upon catalysis by palladium (II) complexes and low carbon monoxide pressures increases with increasing molecular mass of the alcohol, while the selectivity remains virtually the same.
2.
The dilution of the alcohol by acetone does not affect the yields of the carbonylation of 1-nonene in 1-propanol but causes a decrease in this yield in 1-butanol and 1-heptanol. The selectivity decreases upon the addition of acetone to all the alcohols studied.
TL;DR: In this article, the synthesis of oaluminum, gallium, and indium carboranes was reported, which is the first work in the series of carboranyl derivatives of group III elements.
Abstract: Only compounds of boron and thallium have been reported in the series of carboranyl derivatives of group III elements [1-3]. We are the first to report the preparation of oaluminum, gallium, and indium carboranes. The synthesis of C-carboranyl derivatives of AI m Ga, and In was carried out by two methods: I) carboranylation of compounds with a metal-halide bond using C-lithium carboranes and 2) metallation of carborane by alkyl derivatives of AI, Ga, and In in argon (method 2 was also used for thallium derivatives).