Showing papers in "Russian Chemical Bulletin in 1970"
TL;DR: In this article, the authors considered a model where an event of recombination of free atoms or radicals on the surface leads to the appearance of a free electron+free hole pair.
Abstract: 1.
According to the mechanism considered, an event of recombination of free atoms or radicals on the surface leads to the appearance of a free electron+free hole pair. If the subsequent recombination of an electron and a hole, accompanied by emission of a quantum, occurs through the level of the activator, the “basic” band arises. If, however, this recombination occurs through the local level of the chemisorbed atom (radical) itself, the “supplementary” band arises.
2.
The experimental data (dependence of the “basic” band on the nature of the activator and its independence from the nature of the gas, and, conversely, the dependence of the “supplementary” band on the nature of the surrounding medium and its independence from the nature of the activator) fit well into this model.
15 citations
TL;DR: In this article, a series of barene amines was prepared by reducing barenyl-substituted acetonitriles with lithium aluminum hydride, and a barene α-amino-β-barenylpropionic acid was prepared for the first time.
Abstract: 1.
A series of barene amines was prepared by reducing barenyl-substituted acetonitriles and methyl barenylacetamide with lithium aluminum hydride.
2.
Barenecarboxylic and barenylacetic acids do not react with HN3 in the presence of H2SO4.
3.
A bareneα-aminoaeid,α-amino-β-barenylpropionic acid, was prepared for the first time.
4.
4-(Barenylmethyl)thiazole and 4-(barenylmethyI)oxazole were obtained by cyclizingα-barenyl-β-bromoacetone with thioacetamide and acetamide respectively.
5.
1-Phenyl-3-methylbarenylmethylpyrazolone-5, 1-barenylmethyl-3,4-dihydro-6,7-dimethoxyisoquinoline, 1-methylbarenylmethyl-1,2,3,4-tetrahydro-6,7-dimethoxyisoquinoline, and 4-(methylbarenyl)-hydantoin were synthesized.
10 citations
TL;DR: In this paper, the Wagner-Meerwein rearrangement products of isomeric 16β, 17β-oxides of dehydropregnenolone were found to be formed by the cleavage of the C16-O bond.
Abstract: 1.
Acetolysis of the acetate of the 16β, 17β-oxide of dehydroisopregnenolone is accompanied by cleavage mainly at the C17-O bond and formation of rearrangement products, in contrast to the acetate of the 16α, 17α-oxide, where cleavage of the C16-O bond predominates.
2.
Methanolysis of isomeric 16,17-oxides of dehydropregnenolone leads mainly to Wagner-Meerwein rearrangement products.
9 citations
TL;DR: In this paper, a linear dependence of the position of the antisymmetrical valence vibration of the NO2 group on the structure of the substituent was found in a series of nitro compounds.
Abstract: 1.
An analysis of the dependence of the position of the frequencies of the valence vibration of the NO2 group on the structure of the substituent was conducted in a series of nitro compounds. The inductive and steric effects, as well as the effect of conjugation, influence the position of the band of the antisymmetrical valence vibration of the NO2 group.
2.
A linear dependence of the band of the antisymmetrical valence vibration on the induction constant (σ*) of the substituent was found. The position of the band of the symmetrical vibration of the NO2 group is determined chiefly by the steric hindrances of the substituent.
9 citations
TL;DR: When solutions of magnesium chloride and sodium metasilicate, taken in the ratio 6MgCl2∶8Na2SiO3, are poured together, a hydrated magnesium silicate with an admixture of amorphous silica SiO2·nH2O is formed as discussed by the authors.
Abstract: When solutions of magnesium chloride and sodium metasilicate, taken in the ratio 6MgCl2∶8Na2SiO3, are poured together, chiefly a hydrated magnesium silicate with an admixture of amorphous silica SiO2·nH2O is formed.
8 citations
TL;DR: The catalytic activity of binary alloys of palladium with nickel, silver, platinum, and boron with respect to the dehydrogenation of cyclohexane was studied in this paper.
Abstract: 1.
The catalytic activity of palladium and binary alloys of it with nickel, silver, platinum, and boron with respect to the dehydrogenation of cyclohexane was studied.
2.
Increasing the platinum content in the alloys to 1.5% increases their catalytic activity, while increasing the silver content in the range from 20 to 50% reduces their catalytic activity. The alloy of palladium with 5% nickel is more active, while the alloy with 10% nickel is less active than palladium. The apparent activation energy of the dehydrogenation of cyclohexane on all the indicated alloys, with the exception of alloys of palladium with platinum, are close to the value for palladium.
3.
The catalytic activity of the alloys of palladium with boron studied is low and unstable.
7 citations
TL;DR: In this article, new organophosphorus complexones were synthesized: ethylenediaminobisbenzylmethylphosphinic and ethylenobis-o-hydroxynohexylphosphinophosphinic acids.
Abstract: 1.
New organophosphorus complexones were synthesized: ethylenediaminobisbenzylmethylphosphinic and ethylenediaminobis-o-hydroxybenzylmethylphosphinic acids.
2.
The dissociation constants of the indicated acids and the stability constants of their complexes with the ions of certain metals were determined. From a comparison of the complex-forming properties of complexones of three types, containing phosphonic, phosphonous, and phosphinic groups, it was shown that the highest complex-forming ability is possessed by substances with phosphonic groups.
3.
The possibility of spectrophotometric determination of titanium (IV) with ethylenediaminobis-o-hydroxybenzylmethylphosphinic acid was demonstrated.
6 citations
TL;DR: In this article, a method for the production of α-nitro carbonyl compounds by splitting with alkalis the corresponding N-dimethylamino derivatives of α,gb-unsaturated nitro compounds was developed.
Abstract: A method has been developed for the production ofα-nitrocarbonyl compounds by splitting with alkalis the corresponding N-dimethylamino derivatives ofα,gb-unsaturated nitro compounds.
6 citations
TL;DR: In this paper, the authors obtained the UV absorption spectra of 1-phenyl-o-carborane, 3-PNs, 3PNs-O-Carborane (3PNs), 1-PNS-M-CARBane (1,7-Diphenyl-m-CarBane), and also the cesium salt of phenyldi-carbaundecarborane in the 210-340 nm region.
Abstract: 1.
We obtained the UV absorption spectra of 1-phenyl-o-carborane, 3-phenyl-o-carborane, 1-phenyl-m-carborane, 1,2-diphenyl-o-carborane, 1,7-diphenyl-m-carborane, and also the cesium salt of phenyldi-carbaundecarborane (13) in the 210–340 nm region.
2.
The integral intensity of the ∼1600 cm−1 line in the Raman spectra of solutions of 1-phenyl-o-carborane, 1,2-diphenyl-o-carborane, 1-phenyl-m-carborane, and benzotrifluoride in CH2Cl2 was measured.
3.
The effect of the carborane nucleus on the UV absorption band of the benzene ring in the 240–280 nm region is expressed in a slight shift of the maximum, with the retention of a distinct vibrational structure and an increase in the molar absorption coefficient up to several hundred units. In contrast, in the UV spectrum of [C6H5CB9H10CH]−Cs+ the intensity of the same band reaches 7700; the vibrational structure is smoothed out completely.
4.
On the basis of the UV spectra and the intensities in the Raman spectra of the phenylcarboranes it was concluded that conjugation of the benzene ring with carborane nuclei is absent, and that conjugation with the dicarbaundecarborane (13) anion exists.
6 citations
TL;DR: The stretching vibration frequencies of the Si-H bond in substituted silanes containing an Si-N bond depend both on the inductive effect of the substituents and the dπ-pπ, p,σ- and σ, σ-conjugation effects.
Abstract: The stretching vibration frequencies of the Si-H bond in substituted silanes containing an Si-N bond depend both on the inductive effect of the substituents and the dπ-pπ, p,σ- and σ, σ-conjugation effects.
6 citations
TL;DR: The reaction of iminoxyl radicals with chlorine at a low temperature has led to the formation of diamagnetic oxidation products of the radicals as mentioned in this paper, according to the IR and UV spectroscopic data the obtained compounds are 1-oxopiperidinium chlorides.
Abstract: 1.
The reaction of iminoxyl radicals with chlorine at a low temperature has led to the formation of diamagnetic oxidation products of the radicals.
2.
According to the IR and UV spectroscopic data the obtained compounds are 1-oxopiperidinium chlorides.
TL;DR: In this article, the luminescence spectra of chloroform solutions of resins and asphaltenes, isolated from mazut, as well as components extracted from resins with petroleum ether, heptane, and benzene, were measured.
Abstract: 1.
The luminescence spectra of chloroform solutions of resins and asphaltenes, isolated from mazut, as well as components extracted from asphaltenes with petroleum ether, heptane, and benzene, were measured.
2.
The luminescence of solutions of asphaltenes is due to the asphaltenes themselves, and not to resins that might have been adosrbed on the asphaltenes during their isolation from mazut.
3.
The change in the intensities at the maxima of the luminescence spectra with dilution of the asphaltene solutions shows that at various stages of dilution the asphaltenes are in different aggregated states, and this is also manifested in a change in the structure of the luminescence spectra and a deviation of the concentration dependence from the usual one.
TL;DR: Iminoxyl radicals are oxidized at a low temperature by bromine to diamagnetic compounds containing three Bromine atoms as mentioned in this paper, and UV, IR and NMR spectroscopic methods indicated that the obtained compounds are 1-oxopiperidinium salts.
Abstract: 1.
Iminoxyl radicals are oxidized at a low temperature by bromine to diamagnetic compounds containing three bromine atoms.
2.
UV, IR, and NMR spectroscopic methods indicated that the obtained compounds are 1-oxopiperidinium salts.
TL;DR: The main reaction product of isobutylene carbonylation is trimethylacetic acid and its ester, the ratio of these products depending on the reaction temperature and the amount of catalyst as discussed by the authors.
Abstract: 1.
Carbonylation of isobutyl alcohol by carbon monoxide in the presence of boron trifluoride dihydrate leads to formation of trimethylacetic acid and its isobutyl ester, the ratio of these products depending on the reaction temperature and the amount of catalyst.
2.
The main reaction product of isobutylene carbonylation is trimethylacetic acid.
TL;DR: Sanguisorba officinalis L is a plant that produces ursolic acid in the free state in roots of the plant as mentioned in this paper, and the aglycone of the basic glycosides in the plant is a urusolic acid.
Abstract: 1.
19-Dehydroursolic acid occurs in the free state in roots ofSanguisorba officinalis L. The aglycone of the basic glycosides in the plant is ursolic acid.
2.
Sanguisorbin B isβ-L-arabopyranosyl-3-ursolic acid, and sanguisorbin E isβ-L-arabopyranosyl 3-ursano-28-β-(3-acetyl)-D-glucopyranose.
TL;DR: In this paper, a single-stage method involving the action of appropriate N-bromoacetylamino acid esters on 6-benzylmercaptopurine (in dimethyl sulfoxide and in the presence of potassium carbonate) was proposed for the preparation of N-(6-benzinylthio-9H-9-purinylacetic acid (N-PCA)acetyamino esters.
Abstract: 1.
6-Mercaptopurine derivatives containing amino acid residues at the nitrogen of the imidazole ring (N-9) were obtained.
2.
A single-stage method involving the action of the appropriate N-bromoacetylamino acid esters on 6-benzylmercaptopurine (in dimethyl sulfoxide and in the presence of potassium carbonate) was proposed for the preparation of N-(6-benzylthio-9H-9-purinyl)acetylamino esters. Ethyl and benzyl esters of N-(6-benzylthio-9H-9-purinyl)acetylglycine and the corresponding alanine, valine, leucine, and phenylalanine derivatives (VIII a-e and VIII a1-e1) and also the ethyl esters of N-(6-benzylthio-9H-9-purinyl)acetylsarcolysine (VIII f) and the corresponding L-valine derivatives were obtained.
3.
The corresponding N-(6-benzylthio-9H-9-purinyl)acetylamino acids (IX a-f) were obtained from the ethyl esters.
4.
N-(6- Benzylthio-9H-9-purinyl)acetylvaline (IX c) and N-(6-benzylthio-9H-9-purinyl)acetylglycine ethyl ester were obtained from 6-benzylmercaptopurine by the multirange method A through the ethyl ester, hydrazide, and azide of 6-benzylthio-9H-9-purinylacetic acid. A by-product of the reaction (6-benzylthio-9H-9-purinylacetic acid) was isolated.
5.
The ethyl and benzyl esters of N-bromoacetylglycine and the corresponding alanine, valine, leucine, and phenylalanine compounds and the ethyl esters of N-bromoacetylsarcolysine and the corresponding L-valine compounds were obtained as initial products.
TL;DR: The thermodynamic parameters of the cis-trans-transition were determined in this article, and approximately 20% of the dipeptides with a N-methylamide bond have a cis-configuration.
Abstract: 1.
cis-trans-Isomerism of the N-methylamide bond in depeptides containing N-methylalanine residues was studied.
2.
Approximately 20% of the dipeptides with a N-methylamide bond have a cis-configuration.
3.
The thermodynamic parameters of the cis-trans-transition were determined.
TL;DR: The polarographic behavior of dimethylhydrazones and 1,2,4-triazolyl-4-imines of a number of benzaldehydes was studied in buffer solutions with a broad pH range as mentioned in this paper.
Abstract: 1.
The polarographic behavior of dimethylhydrazones and 1,2,4-triazolyl-4-imines of a number of benzaldehydes was studied in buffer solutions with a broad pH range.
2.
A mechanism of the electrode process was proposed.
TL;DR: In this paper, a scheme was proposed for the formation of piperazine from monoethanolamine on the catalyst Co/Al2O3; the individual steps of the catalytic process were described in the terms of coordination chemistry.
Abstract: 1.
During the catalytic synthesis of piperazine from monoethanolamine in the presence of Co/Al2O3, complex compounds are formed.
2.
The product isolated as a result of treatment of the catalyst after the reaction represents a complex of Co3+ with various amines contained in the reaction mixture.
3.
A scheme was proposed for the formation of piperazine from monoethanolamine on the catalyst Co/Al2O3; the individual steps of the catalytic process were described in the terms of coordination chemistry.
TL;DR: In this paper, a new method was proposed for the synthesis of carbomethoxy-substituted derivatives of Mn(Re) π-cyclopentadienyl carbonylnitrosyl.
Abstract: 1.
The fluoborates of Mn(Re) π-cyclopentadienyldicarbonylnitrosyl cations are formed when nitronium tetrafluoborate is reacted with cyclopentadienylmanganesetricarbonyl and cyclopentadienylrheniumtricarbonyl.
2.
A new method was proposed for the synthesis of carbomethoxy-substituted derivatives of Mn(Re) π-cyclopentadienylcarbonylnitrosyl.
3.
Reduction of one of the carbonyl groups of the Re π-cyclopentadienyldicarbonylnitrosyl fluoborate cation to a primary alcohol group occurs when this cation is reacted with sodium borohydride.
TL;DR: The possibility of the formation of a new perperoxide magnesium peroxide Mg (O2)2 at −85 to −65° in the reaction of ozone, dissolved in Freon-12, with a suspended in the same medium, was demonstrated in this article.
Abstract: 1.
The possibility of the formation of a new perperoxide magnesium perperoxide Mg (O2)2 at −85 to −65° in the reaction of ozone, dissolved in Freon-12, with magnesium peroxide, suspended in the same medium, was demonstrated.
2.
Preparations were isolated containing ∼60% Mg(O2)2. The individuality of magnesium perperoxide was confirmed by the EPR method. The limit of its thermal stability −35 to −29° was established by the method of differential thermal analysis.
TL;DR: In this article, the thermal decomposition of α-hydroxyethyl peracetate to peracetic acid and acetaldehyde was studied and the rate constants and activation energy of the decomposition were determined.
Abstract: 1.
α-Hydroxyethyl peracetate (the adduct of peracetic acid with acetaldehyde) reacts extremely readily with cobalt diacetate, whereupon cobalt is converted to the trivalent state.
2.
This reaction plays an important role in the catalytic oxidation of acetaldehyde.
3.
The kinetics of the thermal decomposition ofα-hydroxyethyl peracetate to peracetic acid and acetaldehyde were studied. The rate constants and activation energy of the decomposition were determined.
TL;DR: In this paper, the carbonylation of pentene and 3-methylbutene with CO under pressure in the presence of BF3 hydrates, forming carboxylic acids (the reaction of hydrocarboxylation) was investigated.
Abstract: 1.
The carbonylation of pentene-1 and 3-methylbutene-1 with CO under pressure in the presence of BF3 hydrates, forming carboxylic acids (the reaction of hydrocarboxylation) was investigated.
2.
The reaction in the presence of BF3·1.5H2O proceeds with the formation of a homogeneous mixture, which stratifies into the catalyst and reaction products after the addition of excess water. In the presence of BF3 hydrates and with a larger content of water, at the end of the reaction two layers are obtained: the catalyst and the reaction products.
3.
The most active and selective with respect toα,α,-dialkylcarboxylic acids is BF3·2.5H2O, in the presence of whichα,α-dimethylbutyric acid is formed from pentenes with a yield of 92–93% under the optimum conditions: 100° and 100 atm CO.
TL;DR: In this article, the system gelatin-dextran-water features a low critical blending temperature above the gelling temperature, and the system is shown to be able to handle high temperatures.
Abstract: Above the gelling temperature the system gelatin-dextran-water features a low critical blending temperature.
TL;DR: In this article, the 1:1 recombination product of 3-oxynaphthenyl-2 radical and diphenylpicrylhydrazyl was isolated, assuming that the postulated oxidation mechanism is general for compounds possessing a methylene group bonded to an electron-donating X group and an electron accepting C=O group.
Abstract: Intermediate formation of 3-oxynaphthenyl-2 radical during oxidation of 3-oxythionaphthene to thioindigo was demonstrated by the “inhibitor” method. The 1:1 recombination product of this radical and diphenylpicrylhydrazyl was isolated. It is assumed that the postulated oxidation mechanism is general for compounds possessing a methylene group bonded to an electron-donating X group and an electron-accepting C=O group.
TL;DR: The limits of thermal stability of magnesium peroxide preparations containing up to 75% MgO2 were determined by the method of differential thermal analysis as mentioned in this paper, and it was shown by an interpretation of the thermograms that these preparations release the bulk of the water of the adsorbed mother liquor at 110° and are entirely dehydrated at 260°.
Abstract: 1.
The limits of thermal stability of preparations containing up to 75% MgO2 were determined by the method of differential thermal analysis.
2.
It was shown by an interpretation of the thermograms that these preparations release the bulk of the water of the adsorbed mother liquor at 110° and are entirely dehydrated at 260°. In this case there is a partial decomposition of MgO2 with evolution of oxygen and the formation of Mg(OH)2.
3.
The mixture of MgO2 and Mg(OH)2 formed decomposes exothermic ally within the range 360–375°, liberating oxygen and forming MgO. The following reactions are responsible for the exothermicity of the effect on the heating curves of magnesium peroxide preparations: MgO2+2H2O→Mg(OH)2+H2O2, H2O2→H2O+1/2 O2.
TL;DR: In this paper, the presence of polyene conjugated chains in polypropiolic acids (PPA) facilitates the deearboxylation reaction and leads to a decrease in the effective activation energy.
Abstract: 1.
The presence of a polyene conjugated chain in polypropiolic acids (PPA) facilitates the deearboxylation reaction and leads to a decrease in the effective activation energy from 42.7 kcal/mole for polyacrylic acid to 6–12.5 kcal/mole for PPA.
2.
Polypropiolic acids with different configurations of the polyene chain differ in degree of decarboxylation. The arrangement of the carboxyl groups on both sides of the polyene chain in PPA-(II) prevents interaction of the carboxyls of the neighboring units and promotes an increase in the degree of decarboxylation.
3.
The length of effective conjugation apparently has a substantial influence on the decarboxylation reaction. Increasing the portion of conjugation leads to an increase in the rate and a decrease in the effective activation energy of the decarboxylation process both for homopolymers and for copolymers of propiolic acid.
TL;DR: The 1-hydroxy-o-carboranes react with diazomethane to form 1-methoxy-obarboranes and 1-benzoxy carboranes as mentioned in this paper.
Abstract: 1.
1-Hydroxy-o-earboranes and 1-hydroxy-m-carboranes were synthesized by the reaction of carboranyllithiums with benzoyl peroxide.
2.
The 1-hydroxycarboranes have considerable acidity. The apparent dissociation constants of the 1-hydroxy-o-carboranes and the 1-hydroxy-m-carboranes were measured in 50% alcohol.
3.
The 1-hydroxy-o-carboranes react with diazomethane to form 1-methoxy-o-carboranes.
4.
1-Acetoxy- and 1-benzoxycarboranes were obtained from the 1-hydroxycarboranes.