Showing papers in "Russian Chemical Bulletin in 1972"
TL;DR: In this article, the ionic hydrogenation of acyl derivatives of cyclopentadienylmanganese tricarbonyl was studied, and it was shown that the cyclophane radical stabilizes the neighboring electron-deficient center more strongly than the phenyl ring.
Abstract: 1.
The ionic hydrogenation of acyl derivatives of cyclopentadienylmanganese tricarbonyl was studied.
2.
The ketone group is converted to an alcohol group or a methylene group, depending on the structure of the starting carbonyl compound.
3.
The cyclopentadienylmanganese tricarbonyl radical stabilizes the neighboring electron-deficient center more strongly than the phenyl ring.
16 citations
TL;DR: In this paper, the work functions of the electron in water were determined for 17 metals, as well as those from mercury in alcohols and dimethylformamide, and the values found are correlated with the calculated energies of the nonsolvated electrons in these media.
Abstract: 1.
The work functions of the electron in water were determined for 17 metals, as well as those from mercury in alcohols and dimethylformamide.
2.
The energies of electronic polarization of water, alcohols, and dimethylformamide were calculated. The values found are correlated with the calculated energies of the nonsolvated electrons in these media.
13 citations
TL;DR: In this article, the spectra of some synthetic zeolites (X, Y, A, erionite and mordenite) were studied and an assignment of the absorption bands was made.
Abstract: 1.
The spectra of some synthetic zeolites (X, Y, A, erionite and mordenite) were studied and an assignment of the absorption bands was made.
2.
The character of the IR spectrum is sensitive to the type of zeolite and the SiO2/Al2O3 ratio. Some new data were obtained, which testify to the existence of characteristic “chainlet” vibrations.
12 citations
TL;DR: The condensation of α-hydroxylaminoketones, containing a hydroxylamino group attached to a tertiary carbon atom, with ketones and ammonia led to the formation of 3-imidazoline derivatives.
Abstract: 1.
The condensation ofα-hydroxylaminoketones, containing a hydroxylamino group attached to a tertiary carbon atom, with ketones and ammonia led to the formation of 1-hydroxy-2, 2, 5, 5-tetrasubstituted 3-imidazoline derivatives.
2.
The oxidation of the 1-hydroxy-2,2,5,5-tetrasubstituted 3-imidazolines gave stable iminoxyl radicals.
11 citations
TL;DR: A number of new compounds have been obtained, including the previously inaccessible sterically-hindred 3,6-di-tert-butylcatechol, which has been developed by a method for the selective ortho-alkylation of catechol.
Abstract: 1.
A method for the selective ortho-alkylation of catechol has been developed.
2.
A number of new compounds have been obtained in this way, including the previously inaccessible sterically-hindred 3,6-di-tert-butylcatechol.
10 citations
TL;DR: The synthesis of methyltrichlorosilane by the reaction of silicon with methyl chloride proceeds through stable surface compounds-products of the partial chlorination of silicon (SiCln) as discussed by the authors.
Abstract: 1.
The synthesis of methyltrichlorosilane by the reaction of silicon with methyl chloride proceeds through stable surface compounds-products of the partial chlorination of silicon (SiCln).
2.
Preliminary chlorination of silicon, which leads to the formation of surface compounds (SiCln) as active reaction centers, accelerates the reaction with methyl chloride with the formation of methyltrichlorosilane.
9 citations
TL;DR: In this article, a study was made of the oxidation of complex alicyclic sulfides with hydroperoxides in the presence of molybdenum salts and it was established that hydroperoxide oxidation catalyzed by metals can serve as a convenient method for the preparation of pure sulfoxides and sulfones in high yields.
Abstract: 1.
A study was made of the oxidation of complex alicyclic sulfides with hydroperoxides in the presence of molybdenum salts and it was established that hydroperoxide oxidation catalyzed by metals can serve as a convenient method for the preparation of pure sulfoxides and sulfones in high yields.
2.
Sulfur-containing aromatic heterocycles can be oxidized to sulfoxides and sulfones by treatment with hydroperoxides in the presence of molybdenum compounds, with a clear-cut regulation of the degree of oxidation of the sulfur atoms.
9 citations
TL;DR: In this paper, toluene is reacted with CO2 in the presence of A1C13 at a pressure of 20-50 atm and temperatures of 77-125°, and carboxylated to p-toluic acid in up to 23% yield.
Abstract: 1.
When toluene is reacted with CO2 in the presence of A1C13 at a pressure of 20–50 atm and temperatures of 77–125° the toluene is carboxylated to p-toluic acid in up to 23% yield. At the same time are formed ditolyl ketones in up to 35% yield and benzene in up to 16% yield.
2.
Disproportionation of the toluene to benzene and xylenes occurs during the indicated reaction, and also the formation of ditolyl ketones via toluic acid.
7 citations
TL;DR: In this article, an expression was obtained for the distribution of the concentrations along the length of the layer of the adsorbent grains for short times, considering the effect of longitudinal diffusion.
Abstract: 1.
An expression was obtained for the distribution of the concentrations along the length of the layer of the adsorbent grains for short times, considering the effect of longitudinal diffusion.
2.
A method was proposed for determining the coefficient of external mass exchange according to the known coefficient of longitudinal diffusion and the known distribution of breakthrough concentrations along the layer.
3.
A formula describing the initial portion of the effluent curves (region of low concentrations) in the system of a stationary front was found.
4.
In accord with the experimental data, the region of low concentrations of the effluent curve can be represented in the coordinates of the logarithm of the relative concentration versus the time in the form of a straight line.
5.
The approximate equations of internal diffusion kinetics are discussed.
7 citations
TL;DR: In this article, the oxidation reduction potentials of a number of systems of the amino complexes of platinum were measured, and it was shown that the systems containing the dihydroxo complexes of Pt(IV) are irreversible.
Abstract: 1.
The oxidation-reduction potentials of a number of systems of the amino complexes of platinum were measured. It was shown that the systems containing the dihydroxo complexes of Pt(IV) are irreversible.
2.
The dependence of the potentials of systems containing the dihalo complexes of Pt(IV) on the temperature in the range 10–50° was investigated; a study was made of the effect of the stability of the complex and the nature of the coordinated groups on the value of the potential; a thermodynamic characterization of the processes was given.
6 citations
TL;DR: In this paper, a simple and safe method was proposed for the synthesis of 3methyl-4-nitrofuroxan, and the thermochemical, enthalpy, and detonation characteristics of this compound were determined experimentally.
Abstract: 1.
A simple and safe method was proposed for the synthesis of 3-methyl-4-nitrofuroxan.
2.
The thermochemical (heat of combustion, enthalpy of formation) and detonation (explosion heat, detonation rate, density of a monocrystal) characteristics of this compound were determined experimentally.
TL;DR: In this paper, the authors investigated the sequence of hydrogenation of carvone on platinum and palladium catalysts and found that carvacrol is formed as a result of parallel reactions of isomerization and irreversible catalysis.
Abstract: 1.
The sequence of hydrogenation of carvone on platinum and palladium catalysts was investigated.
2.
The hydrogenation of carvone on Pd-black proceeds nonselectively with the formation of carvotanacetone and carvomenthone. As a result of parallel reactions of isomerization and irreversible catalysis, carvacrol is formed. Palladium on carbon catalyzes the process differently from Pd-black.
3.
Hydrogenation of carvone on Pt-black proceeds selectively through the successive formation of carvotanacetone, isomeric carvomenthones, and isomeric carvomenthols.
TL;DR: In this paper, the silylation of dimethyl nitromalonate with trimethylchlorosilane leads to the trimethylsilyl ester of dicarbomethoxymethanenitronic acid, which is more stable then its alkyl analogs.
Abstract: 1.
The silylation of dimethyl nitromalonate with N, N′-diphenyl-N-trimethylsilylurea, and also of the Ag salt of dimethyl nitromalonate with trimethylchlorosilane, leads to the trimethylsilyl ester of dicarbomethoxymethanenitronic acid, which is more stable then its alkyl analogs, and which reacts with amines, acids and alcohols by a common scheme to give dimethyl nitromalonate and the corresponding trimethylsilyl derivatives.
2.
The trimethylsilyl ester of dicarbomethoxymethanenitronic acid enters into the 1, 3-dipolar cycloaddition reaction with styrene and methyl acrylate, forming the corresponding 5-substituted N-trimethylsilyloxy-3, 3-biscarbomethoxyisoxazolidines, in which connection the reaction is structurally and spatially selective, and leads to the stereoisomer with the same mutual orientation of the substituent in the 5 position and the -OSi(CH3)3 group.
3.
The inversion of the nitrogen in the obtained 5-substituted N-trimethylsilyloxy-3, 3-biscarbomethoxyisoxazolidines is hindered below 100°, whereas equilibrium mixtures of the stereoisomers are formed when the compounds are heated at a higher temperature.
4.
Treatment of the 5-substituted N-trimethylsilyloxy-3, 3-biscarbomethoxyisoxazolidines with CH3·ONa gives the 5-substituted 3-carbomethoxyisoxazolines, and also methoxytrimethylsilane and the Na salt of monomethyl carbonate.
TL;DR: In this article, the azocoupling of 3-hydroxyquinoline and 4-hydroxisoquinoline was investigated, and the azo-group in 3-hexoxyquinoline is a substituent in the 4-position of the quinoline ring.
Abstract: 1.
The azocoupling of 3-hydroxyquinoline and 4-hydroxyisoquinoline was investigated.
2.
The azo-group in 3-hydroxyquinoline is a substituent in the 4-position of the quinoline ring.
3.
Azocoupling of 4-hydroxyisoquinoline is initially directed in the 3-position and then in the 1-position of the isoquinoline ring.
TL;DR: This method has been used p rev iously to obtain 2 -amino imidazo les [2] and has achieved 60-90% yields in the f i r s t s tep a r e c o r l e s s, c rys t a l i zab le subs tances as mentioned in this paper.
Abstract: This method has been used p rev ious ly to obtain 2 -amino imidazo les [2]. The t r i azenes fo rmed in 60-90% yields in the f i r s t s tep a r e c o l o r l e s s , c rys t a l l i zab le subs tances (R = CHa, mp 100 ~ Found: C 38.90; H 6.98; 13 39.50; N 15.00%. CaBIoH19N 3. Calculated: C 39.00; H 6.85; ]3 39.00; N 15.15%. R = C6H5, mp 114 ~ Found: C 49.70; H 6.14; ]3 32.00; N 12.25%. CllB10H21N 3. Calculated: C 49.50; H 6.25; B 31.80; N 12.45). React ion with ca rborany l l i th ium gave a mix ture of monot r iazene (rap 96 ~ Found: C 36.92; H 6.20; ]3 40.71; N 15.76%. CaBIoH17N 3. Calculated: C 36.54; H 6.46; B 41.00; N 16.00~o) and b i s t r i azene (mp 134 ~ Found: C 43.81; H 6.40; 13 27.95; N 21.30%. C14B10H22N 6. Calculated: C 44.00; H 5.75; B 28.15; N 22.10%). The overa l l yield was 80%. The b i s t r i azene was obtained in 85% yield f r o m the dil i thium der iva t ive . An intense absorpt ion band is obse rved at 3295 cm -1 in the IR s pe c t r a of all of the compounds. The posit ion of the hydrogen a tom in the t r i azene s y s t e m was not es tab l i shed . The cor responding amines a re fo rmed in 60% yields on t r e a t ment of the t r i azenes with HC1-methano l (1:1) at 50-60 ~ Intense absorpt ion bands a r e observed at "~3380 and 3460 cm -1 in the IR s pec t r a of the amines .
TL;DR: In this article, a method of interlinked oxidation of hydrocarbon with alcohol in the presence of a selective inhibitor is proposed for the measurement of the rate constant of the reaction of the peroxy radical with primary or secondary alcohols.
Abstract: 1.
A method of interlinked oxidation of hydrocarbon with alcohol in the presence of a selective inhibitor is proposed for the measurement of the rate constant of the reaction of the peroxy radical with primary or secondary alcohols.
2.
This method was used to measure the rate constants for the reaction of cyclohexenylperoxy radicals with benzyl alcohol, cyclohexanol, isopropyl alcohol, n-butanol, and ethanol at 60° and methanol at 40°.
TL;DR: In this paper, it was shown with a high degree of accuracy that the density and refractive index in a homologous series of organic compounds are related by a linear function.
Abstract: It was shown with a high degree of accuracy that the density and refractive index in a homologous series of organic compounds are related by a linear function.
TL;DR: Very strong asymmetrization of the electron distribution on the central atom occurs for unsymmetrically substituted compounds of trivalent antimony, which is expressed in a noticeable increase of the asymmetry parameter and the constants of the quadrupole bond for121Sb and123Sb when compared with compounds of the SbX3 type as discussed by the authors.
Abstract: Very strong asymmetrization of the electron distribution on the central atom occurs for the unsymmetrically substituted compounds of trivalent antimony, which is expressed in a noticeable increase of the asymmetry parameter and the constants of the quadrupole bond for121Sb and123Sb when compared with compounds of the SbX3 type.
TL;DR: In this paper, iron tetracarbonyl and diiron hexacarbonyl complexes are formed when pyridazine and 3,6-dimethylpyridine are reacted with iron carbonyls.
Abstract: Iron tetracarbonyl and diiron hexacarbonyl complexes are formed when pyridazine and 3,6-dimethylpyridazine are reacted with iron carbonyls.
TL;DR: In this article, an analysis of the experimental data on the decomposition of aliphatic nitro compounds reveals fine effects of the influence of the structure of the molecule on the preexponential factor of the reaction rate constant.
Abstract: An analysis of the experimental data on the decomposition of aliphatic nitro compounds reveals fine effects of the influence of the structure of the molecule on the preexponential factor of the reaction rate constant. The value of the latter depends on the contribution of three factors, manifested in the formation of the activated complex: liberation of the internal rotation relative to the dissociating C-N bond, a decrease in the frequencies of the deformational vibrations associated with this bond, and rotation of the alkyl groups next to the reaction center.
TL;DR: The direct o-fluorination of the dimethyl- and diethylanilines was accomplished by treatment with perfluoropiperidine, and it was shown that this reaction has a one-electron character.
Abstract: The direct o-fluorination of the dimethyl- and diethylanilines was accomplished by treatment with perfluoropiperidine, and it was shown that this reaction has a one-electron character
TL;DR: The chlorination of 2,4-bis(trifluoromethyl)-3-methoxy-1,1, 1,5, 5, 5-hexafluoro-2-pentene proceeds as the replacement of one hydrogen atom of the methyl group by chlorine and the subsequent addition of chlorine to the double bond, which leads to the formation of 1,1-3,3-tetrakis(trifi-ormethyl)chloroacetone.
Abstract: 1.
A number of saturated fluorine-containing ethers was synthesized by photochemical chlorination.
2.
The chlorination of 2,4-bis(trifluoromethyl)-3-methoxy-1,1,1,5,5,5-hexafluoro-2-pentene proceeds as the replacement of one hydrogen atom of the methyl group by chlorine and the subsequent addition of chlorine to the double bond, which leads to the formation of 1,1,3,3-tetrakis(trifluoromethyl)chloroacetone.
3.
When ethers, containing the -CF2OCCl3 group, are treated with antimony trifluoride the chlorine atoms are smoothly replaced by fluorine. At the same time, ethers containing the -CFClOCC13 group undergo decomposition as the result of cleavage of the C-O bond.
TL;DR: The electronic influence of 1-6dicarbalkosodecaborane(10) and 1-10-dicaralkosoda-decaborane (10) groups, which play the role of weak electron acceptor groups, is manifested mainly according to an inductive mechanism.
Abstract: 1.
The electronic influence of the 1-[1,6-dicarbalkosodecaborane(10)] (induction constant σi=0.10 and resonance constant σR0=−0.02) and 1-[1,10-dicarbalkosodecaborane(10)] groups (σi=0.05 and σR0=−0.02), which play the role of weak electron-acceptor groups, is manifested chiefly according to an inductive mechanism.
2.
The nitration of 1-phenyl-1,10-dicarbalkosodecaborane(10) proceeds primarily in the p-position of the benzene ring.
TL;DR: In this paper, a simple route to the synthesis of vinylogs of the diesters and nitriles of terephthalic acid and 1,4-diaroylbenzenes is proposed.
Abstract: 1.
A simple route to the synthesis of vinylogs of the diesters and nitriles of terephthalic acid and 1,4-diaroylbenzenes is proposed.
2.
The IR and UV spectra of the compounds obtained are compared with those of their linear analogs.
TL;DR: In this article, it was shown that a direct reaction of the intermediate or starting chlorine-containing iron compound with electrophilic CCl3(CH2CHCl)n radicals is possible via the mechanism of ligand transfer.
Abstract: 1.
In the radical telomerization of vinyl chloride with CCl4, catalyzed by Fe(CO)5, Fe(AA)3 or FeCl3, the yield of the adduct increases when compared with peroxide initiation. The amount of the adduct passes through a maximum when the catalyst concentration is increased. An increase in the relative yield of the higher telomer homologs, as well as a reduction in the telomerization rate, is observed in the presence of Fe(CO)5 or FeCl3 when dilution is with methanol.
2.
It was shown that direct reaction of the intermediate or starting chlorine-containing iron compound with electrophilic CCl3(CH2CHCl)n. radicals is possible via the mechanism of ligand transfer.