Corresponding Member of the Academy of Sciences of the USSR N. N. VOROZHTSOV, Jr., and V. Ya. RODIONOV
This paper reexamines the identity of the red compound of formula C10H6S2 obtained by passing naphthalene and sulfur vapors through a red-hot iron tube, previously assigned to thienothiophthene or thienothionaphthene structures. The authors repeated the reaction, isolated the product, and compared i…
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This paper examines how hydrogenation affects the viscosity of alkyl aromatic hydrocarbons with isolated benzene rings and compares them with their naphthenic analogs. Using viscosity measurements at several temperatures for C24 bicyclic and related structures, the authors distinguish hydrocarbons w…
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This paper examines the unusual selectivity of zinc catalysts in hydrogenation reactions, contrasting it with the behavior of nickel and other metallic catalysts. Using approximate bond energy calculations for intermediate surface complexes, the authors estimate energy barriers for hydrogenation of …
and Corresponding Member of the Academy of Sciences of the USSR A. D. PETROV
This study examines the mechanism of silicon hydride addition to unsaturated compounds in the presence of platinized carbon and chloroplatinic acid, arguing against a purely heterolytic interpretation. Using diphenylpicrylhydrazyl as a radical trap and deuterium exchange experiments between ethyldic…
L. L. Gordienko, A. I. Brodskii
This study examines nitrogen isotopic exchange between ammonia and acid amides, focusing on how substituents, radical structure, and ammonium chloride affect the exchange rate. Kinetic measurements for aliphatic and substituted aromatic amides show that exchange is accelerated by increased electroph…
E. M. Rokhlin, N. P. Gambaryan, and Academician I. L. Knunyants
This paper examines the unusual mobility and saponification of fluorine atoms in the trifluoromethyl groups of α-benzamidohexafluorodimethylacrylic acid and related esters. The authors report that treatment with sodium bicarbonate at room temperature converts the acid and its esters into derivatives…
T. I. MALINOVSKII, I. D. SAMUS’, and Academician N. V. BELOV
Corresponding Member of the Academy of Sciences of the USSR K. A. ANDRIANOV, A. A. ZHDANOV, and V. A. ODINETS
This paper examines the chloromethylation of benzyldimethylchlorosilane as a route to chloromethylbenzyldimethylchlorosilane and related organosilicon derivatives. The authors show that the reaction proceeds effectively in fuming hydrochloric acid with paraformaldehyde and without a catalyst, while …
Z. N. Parnes, V.-Zh. Zdanovich
The study examines how substituent effects are transmitted through different conjugated systems by measuring the rate of isotopic hydrogen exchange at the methyl group of para-substituted benzalacetophenones and 4'-acetyldiphenyls. Rate constants were determined in deuteroethanol with sodium ethoxid…
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This study uses oxygen-18 labeling to examine the mechanism of the anthranilic rearrangement, focusing on whether the carboxyl oxygen atoms in anthranilic acid derive from the nitro compound or from aqueous alkali. Reactions of o-nitrotoluene and the potassium salt of o-nitrotoluene-p-sulfonic acid …
S. G. MAIRANOVSKII, V. A. PONOMARENKO, N. V. BARASHKOVA
This study examines the polarographic behavior of several iodomethyltrialkylsilanes and iodomethyldimethylphenylsilane in aqueous ethanol, comparing them with primary iodoalkanes to assess the influence of silyl substituents on electrochemical cleavage of the adjacent C-I bond. The compounds gave ir…
I. Ya. POSTOVSKII, N. F. KAZARINOVA, G. B. AFANAS’EVA, and N. I. LATOSH
The paper reports the synthesis of new beta-aminoethyl esters of dithiocarbamic acids, motivated by structural analogy to beta-aminoethylisothiuronium bromide and by interest in physiologically active quinone derivatives. Beta-chloroethylamine was reacted with sodium salts of diethyl-, tetramethylen…
A. K. Zefirova, N. N. Tikhomirova, A. E. Shilov
The study examines products formed by reactions of aluminum alkyls and aryls with dicyclopentadienyltitanium(IV) halides, using electron paramagnetic resonance spectra as the principal structural probe. Variation of the aluminum to titanium ratio showed distinct spectral transitions for hydride-cont…
Corresponding Member of the Academy of Sciences of the USSR O. A. REUTOV and I. P. BELETSKAYA
This paper examines the mechanism of bimolecular electrophilic substitution at a saturated carbon atom using the symmetrization and isotopic exchange reactions of alpha-bromomercuriphenylacetic acid esters as model systems. On the basis of kinetic and stereochemical evidence, the authors argue for a…
Academician B. A. KAZANSKII, A. L. LIBERMAN, and N. I. TYUN’KINA
This study examines whether stereoisomeric 1,4-di-tert-butylcyclohexanes conform to the Auwers-Skita rule, which relates physical constants to cis and trans configurations in cyclic compounds. The authors synthesized 1,4-di-tert-butylbenzene, hydrogenated it over Raney nickel, separated the resultin…
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Radiothermoluminescence was investigated in irradiated organic compounds, with emphasis on polymers and hydrocarbons, to assess whether glow curves reflect structural transitions. Samples were irradiated at about 100 K with 1.5 MeV electrons, stored in liquid nitrogen, and heated at a constant rate …
V. E. KAZARINOV and N. A. BALASHOVA
This study investigates iodine adsorption on smooth platinum from acidic and alkaline iodide solutions, and its desorption under varied electrochemical conditions, using tracer atoms with purified iodine isotopes and radioactive platinum. The authors show that commercial carrier-free iodine isotope …
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The study examines the reaction of dialkylphosphorous acids with p-benzoquinone and alpha-naphthoquinone, motivated by interest in organophosphorus compounds that might combine lubricant additive properties with antioxidant functionality. Using equimolar reactants in the presence of sodium alcoholat…
V. A. PONOMARENKO, A. D. SNEGOVA, M. R. PITINA
This study examines the continuous high-temperature gas-phase chlorination of phenyltrichlorosilane with chlorine at 350 to 450 degrees Celsius using quartz or activated carbon packing. The reaction gave monochlorophenyltrichlorosilanes along with smaller amounts of polychlorinated products, and the…
It is generally known that tautomerism may occur in amides of carboxylic acids,
This paper addresses the unresolved question of lactam, lactim tautomerism in carboxylic acid amides. Using ultraviolet rotatory dispersion measurements on optically active alpha-phenylethylamine derivatives, the authors compare solvent effects in benzene and methanol and find that N-benzoyl-alpha-p…
A. K. AREN, B. E. AREN, and Academician of the Academy of Sciences of the Latvian SSR G. Ya. VANAG
This paper describes a method for preparing 2-arylideneindandiones-1,3, compounds used as intermediates in syntheses of polycyclic systems and nucleophilic addition products. Instead of isolating indandione-1,3 and condensing it with aromatic aldehydes, the method generates indandione-1,3 in situ fr…
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This study examines the gamma-radiation reduction of ferric ions in acid solutions saturated with hydrogen under pressure, aiming to clarify the roles of hydrogen, ferric ion concentration, and acid composition in the radiolysis mechanism. Measurements of initial ferrous ion yields were made in sulf…
Academician A. V. TOPCHIEV, L. S. POLAK, N. Ya. CHERNYAK, V. E. GLUSHEV,
This paper examines radiation-thermal cracking of hydrocarbons as a means of combining radiation initiation with elevated temperature to promote chain cracking reactions and increase useful product yields. Experiments on vapor-phase n-heptane, irradiated mainly with 900 keV electrons and compared wi…
I. E. NEIMARK, V. M. CHERTOV, R. Yu. SHEINFAIN, and N. S. KRUGLIKOVA
This study examines whether silica gel can be given selective basic adsorption properties by chemically modifying its surface hydroxyl groups with amino alcohols. Macroporous hydrated silica gel was treated with monoethanolamine, diethanolamine, or triethanolamine under reflux or autoclave condition…
A. N. Sergeeva and K. N. Mikhalevich
This paper reports the synthesis and characterization of a sulfur-containing mixed cyano complex of trivalent cobalt, potassium disulfotricyanoaquo-cobaltate, prepared by reacting potassium hydroxopentacyanocobaltate with potassium sulfide in aqueous solution. The reaction produced dark amber rhombi…
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This study examines the product composition and mechanism of gaseous alkane cracking initiated by small additions of azomethane, focusing on propane, n-butane, and isobutane. Product mixtures obtained under conditions where the alkanes do not crack appreciably on their own were analyzed by gas chrom…
B. V. IOFFE and K. N. ZELENIN
This paper reports an unexpected rearrangement observed during attempted condensation of unsymmetrical dialkylhydrazines with acrolein to form unsaturated hydrazones. Under cold, weakly acidic aqueous conditions, dimethylhydrazine and diethylhydrazine instead gave the corresponding beta-dialkylamino…
Corresponding Member of the Academy of Sciences of the USSR A. D. PETROV, G. I. NIKISHIN, and G. V. SOMOV
This paper describes a high-temperature method for introducing trichlorovinyl and related chlorovinyl groups into aromatic hydrocarbons and olefins by passing mixtures with tetrachloroethylene, or in some cases trichloroethylene, through an empty quartz tube at about 550 to 590°C. The authors propos…
and N. A. PREOBRAZHENSKII
This study examines pH-dependent isomeric transformations in meso-carbethoxymethyl-substituted dipyrrylmethenes, focusing on the origin of their differently colored forms. A series of compounds with carbethoxy substituents in different ring positions was prepared and analyzed by electronic absorptio…
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This paper examines why polarographic catalytic and kinetic waves limited by a preceding chemical reaction show a decrease in current at more negative potentials. It argues that the observed wave shape results from the changing adsorption of the electrochemically inactive catalyst form on the mercur…
V. L. Vaister, V. D. Ryabov, and B. M. Piryatinskii
This paper proposes catalytic cracking of dioxyarylalkanes over aluminosilicate catalysts as a route to vinylphenols, a class of reactive monomers whose synthesis had been difficult or only slightly studied. The authors examine the cracking of 1,1-(4,4-dioxy)-diphenylethane, its dimethyl analogue, a…
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The study examines how solution acidity affects the anodic dissolution and cathodic deposition processes of indium amalgam in perchloric acid solutions. Using polarization measurements combined with a radiochemical method on a stationary 0.1 M indium amalgam electrode, the authors measured true anod…
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This study examines the reduction of stoichiometric manganese ferrite by hydrogen and by graphite, including the effect of potassium and sodium carbonate additives. Ferrite prepared by sintering iron and manganese oxides in carbon dioxide was reduced under controlled conditions, with reaction progre…
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This paper examines reactions of aldehydes and ketones, especially halogen-substituted carbonyl compounds, with amides of phosphorous acids. Extending earlier work on phosphorous esters and anilides, the authors propose that diethylamides of phosphorous acids react through nucleophilic attack by pho…
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This study examines how chromium content affects the electrochemical and corrosion behavior of iron-chromium alloys, with particular attention to the often cited 13 percent chromium boundary for corrosion resistance. Using potentiostatic measurements combined with colorimetric determination of disso…
A. V. BOGDANOVA, Corresponding Member of the Academy of Sciences of the USSR M. F. SHOSTAKOVSKII
This paper investigates the synthesis and reactions of unsaturated ether acetals, thioether acetals, and mercaptals containing conjugated enyne systems. Ethynylvinyl ethers and thioethers were converted through magnesium-organic complexes and ethyl orthoformate into diethyl acetals of substituted pe…
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This paper develops general kinetic equations for nonchain monomolecular radiation-chemical reactions involving an initial substance with two possible excited states and multiple decomposition pathways. Using stationary-state balances for excited species, it derives rate expressions for small, mediu…
Corresponding Member of the Academy of Sciences of the USSR S. Z. Roginskii and Yu. L. Khait
This paper examines the compensation effect in chemical kinetics, the observed correlation between the Arrhenius pre-exponential factor and activation energy, especially in condensed phases and catalytic processes. After reviewing limitations of earlier explanations, the authors develop a statistica…
Academician Vikt. I. SPITSYN, E. A. TORCHENKOVA, and I. N. GLAZKOVA
This study examines how the beta radiation of sulfur-35 labeled barium sulfate affects its dissolution kinetics and apparent solubility in water. Radioactive barium sulfate preparations of varying specific activity were precipitated under different reagent conditions, then stirred with water at 20 d…
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This paper examines whether aromatic amine ligands alter the coordination number and crystal structure of cadmium halide addition products, a question motivated by molecular orbital arguments about bonding in transition metal complexes. The authors synthesize and analyze cadmium iodide dianiline, Cd…
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Cesium halide vapors were examined by mass spectrometry to determine whether they contain associated molecules and to measure the dissociation energies of the corresponding dimers. Using an MS-4 mass spectrometer with a double effusion chamber, the study recorded ion currents for cesium fluoride, ch…
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This study examines how potassium bromide and tetraalkylammonium bromides influence the differential capacitance of the mercury double layer in aqueous butyl alcohol solutions. Measurements were made with a dropping mercury electrode by an impedance bridge method at 750 cps, varying electrolyte conc…
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This paper examines how spatially structured liquids with high effective viscosity, such as bitumens and tars, behave during emulsification with aqueous solutions of hydrophilic surfactants. Using bitumen B-5 and related systems, the authors compare direct and inverse emulsion formation as a functio…
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This study examines the alkaline cleavage of mono- and diquaternary salts of 1,4-di(dimethylamino)-2-methylbutene-2 to determine the course of formation of conjugated dienamines. By comparing cleavage products from iodide, phenylammonium, and butynylammonium salts under aqueous alkali and vacuum con…
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The paper examines the acid-induced rearrangement of 1,2′-hydrazonaphthalene, with particular attention to the unexpected formation of appreciable amounts of 4-amino-1,2′-dinaphthylamine, an n-semidine. Experiments varying acid, concentration, solvent, and phase conditions show that when most of the…
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This study reports the synthesis of previously undescribed aryl esters of methane- and ethanethiosulfonic acids and evaluates their antimicrobial properties. The compounds were prepared by reacting sodium salts of the corresponding alkanesulfinic acids with arenesulfenyl chlorides bearing hydrogen, …
L. M. ROEV
This paper reports the appearance of broad, nonselective infrared absorption backgrounds when various vapors are adsorbed on solid adsorbents such as alumogel, oxides, silica, and calcium fluoride. Measurements across multiple adsorbent and adsorbate systems show that the decrease in transparency de…
A. V. ABLOV, M. P. FILIPPOV, and N. M. SAMUS’
This paper examines the possible existence of cis and trans forms of diaquo-bis-dimethylglyoximatocobaltic salts, prompted by unexpected differences in absorption spectra of related hydroxo and dihydroxo cobalt dimethylglyoxime complexes under acidic and alkaline conditions. Using spectrophotometric…
V. B. RATINOV and O. M. TODES
This paper develops a treatment of spontaneous crystallization from supersaturated solutions of dissociated salts by modifying classical nucleation expressions to use the concentrations, or activities, of the dissociated ions rather than the total salt concentration. The authors derive relations bet…