α-Ketothioketene dimers

Conclusions When,-dichlorovinyl ketones are reacted with Na₂S, NaSC(S)N(C₂H₅)₂, KSC(S)OC₂H₅, and NaSCOCH₃, two types of sulfur-containing heterocyclic compounds are formed: 1,3-dithietanes and 1,3-dithiols , at which time the ratio of the products depends on the nature of the sulfur-containing nucleophilic reagent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2940–2048, September, 1976.     

Reaction of silicon hydrides with primary aliphatic amines

Conclusions The direction of the reaction of the silicon hydrides: R₂SiH₂, RSiH₃, and with primary aliphatic amines, in the presence of catalysts based on Group VIII compounds, as a function of the structure of the silicon hydride and the nature of the employed catalyst, was established.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2330–2333, October, 1972.     

Thermische Umlagerung von Acetoxy-cyclohexadienonen, 2. Mitt.

Zusammenfassung Es wird die Frage untersucht, ob bei der thermischen Umlagerung von entsprechend allyl-substituierten o-Benzochinol-acetaten der Allyl- oder der Acetoxylrest rascher wandert. Das 2-Allyl-2-acetoxy-cyclohexadienon liefert bei der genannten Reaktion (es sind schon Temperaturen um 100° ausreichend) überwiegend ein Monoacetat des 4-Allylbrenzcatechins. Damit ist bewiesen, daß der Rest rascher als der Rest in die p-Stellung zur Carbonylgruppe des Chinolacetates wandert. Eine Wanderung des Acetoxylrestes in die o- oder in die p-Stellung zur Carbonylgruppe, welche zur Bildung von 3-Allyl-brenzcatechin bzw. 2-Allylhydrochinon führen müßte, konnte nicht beobachtet werden. Entsprechend liefert das 2,6-Diallyl-2-acetoxy-cyclohexadienon bei der thermischen Umlagerung überwiegend ein Monoacetat des 3,5-Diallyl-brenzcatechins. Nach einem anderen Mechanismus verläuft die Umlagerung des 2-Methyl-6-allyl-2-acetoxy-cyclohexadienons. Es entsteht neben wenig 2-Methyl-6-allyl-hydrochinon in der Hauptmenge ein Monoacetat des 3-Methyl-5-allyl-brenzcatechins. Es wird also die Allylgruppe durch den in die o-Stellung wandernden Acetoxylrest verdrängt. Auf diese Reaktion wird näher eingegangen, weil sie in engem Zusammenhang mit der Frage steht, ob ganz allgemein eine Umlagerung von o-Chinolacetaten vom Typ in die Isomeren möglich ist.Mit 2 AbbildungenHerrn Prof. Dr.F. Feigl zum 70. Geburtstag in alter Freundschaft!F. W. E. Zbiral, F. Wessely undE. Lahrmann, (gilt als 1. Mitt. dieser Reihe), Mh. Chem.91, 331 (1960).     

Telomerization of propylene with methyl propionate

Conclusions The principal products of the telomerization of propylene with methyl propionate are telomers with the structure , where n=1–4.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2534–2537, November, 1973.     

Character of intermediate radicals in homolytic isomerization of cyclic acetals and their heteroanalogs

Conclusions Employing the EPR method and 2-methyl-2-nitrosopropane as the spin trap, we recorded the formation of the radicals (n = 1 and 2; X = O, N, or a chain composed of C and O atoms; R = H or alkyl) during the photolysis of acetals and their heteroanalogs in the presence of di-tertbutyl peroxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2097–2099, September, 1976.The authors are indebted to A. Sh. Mukhtarov for assistance in running the experiments.     

Reaction of 8-(dimethylamino)methyl-1-naphthyl phenyl silanethione with phosphorus ylides

The title silanethione reacts with phosphorus ylides under conditions of kinetic control to give betaines containing a linear fragment. Under conditions of thermodynamic control, the derivatives of phosphonium 1-silaacenaphthene-1-thiolate are formed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2140–2141, December, 1993.     

Synthesis and properties of polyamides and polyamidoesters based on bis-[N-alkyl-(or aryl-)aminomethyl]-phosphonic acids

Conclusions The activity of bis-[N-alkyl-(or aryl)-aminomethyl] phosphonic acids of the general formula (RNHCH₂)₂ in the interfacial polycondensation reaction with bisphenol A has been studied.In their activity the diamines studied can be placed in the following series: R=C₆H₅CH₂, C₄H₉, C₆H₅, C₃H₇.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 633–636, March, 1969.     

Complexes of rhodium carbonylchloride and phosphorus(iii) cyanides in mediated electrochemical reduction of 2-carbomethoxy-2-methyl-1,1-dichlorocyclopropane

Electrochemical reduction of the complexes Rh(CO)ClL₂ [L = (EtO)₂PCN (1), Ph₂PCN (2)] and Rh₂(CO)₄L [L = P(CN)₃ (3), (4)] and their catalytic properties in electrochemical reduction of 2-carbomethoxy-2-methyl-1,1-dichloro-cyclopropane were studied. The catalytic electroreduction of a substrate at the reduction potentials of the central ion was developed for complexes2–4. This process is accelerated substantially for complexes2 and3 in the presence of anthracene.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1970–1972, October, 1995.     

Structure of nitramine salts

Conclusions The previously proposed structure for the salts of primary nitramines was corro-borated on the basis of the vibrational spectra and quantum-chemical calculations.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 948–950, April, 1972.The authors wish to thank S. Gagarin, who took part in the calculations.     

Determination of azoxy groups in polyazopolyarenes

Conclusions The band in the 1270–1280 cm^–3 region, corresponding to the vibrations of the -C -N=bond in the grouping , can be used to determine the presence of azoxy groups in polyazopolyarenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2623–2625, November, 1970.     

Hydrogen bonds and protonation of carbonyl-containing polynuclear rhodium complexes

According to IR spectroscopy data, the interaction of bi-, tri-, and tetranuclear cyclopentadienylcarbonyl rhodium complexes with rather weak protic acids (phenols, fluoroalcohols) in low-polarity media results in the formation of hydrogen bonds of the OH...O=C type with bridged carbonyl groups. According to¹H NMR data, protonation of these complexes with strong acids (CF₃COOH and HBF₄) occurs at the the Rh-Rh bond to give the symmetrical bridge.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 386–388, February, 1995.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-0461).     

Chemistry of 1,1,2,2-tetracyanoethane. Communication 13. Stereochemistry and structure of 5-methyl-3-(1-methyl-3-isopropoxyallyl)-1-formyl-3,4,4-tricyano-1-cyclopentene

The structure of 5-methyl-3-(1-methyl-3-isopropoxyallyl)-1-formyl-3,4,4-tricyano-1-cyclopentene was determined by an x-ray diffraction structural analysis. A discussion was given for the pseudoaxial orientation of the CN and C-H groups at the 3,5-positions, steric strain, the effect of this strain leading to a large ring flexure angle and extension of the C-C bonds, the bipolar nature of the enaminoformyl fragment, twisting of the NH₂ group due to an unusual intramolecular hydrogen bond involving the ethereal oxygen atom, the lack of extension of the bond under conditions of n_p(O)–^*(C=C) conjugation, and the conformation of the isopropyl group relative to the O-C(sp³) bond.Communication 12, see our previous work [1].Institute of Chemical Physics, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 108–113, September–October, 1989.     

PMR investigation of internal inhibited rotation in N1,N1-dimethyl-N2-trifluoro[chloro]acetylamidines of picolinic and nicotinic acids

Summary Hindered rotation around the bond in the N-acylamidines has been investigated by PMR spectroscopy, and the kinetic parameters of the hindered rotation have been determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 758–762, April, 1981.     

Telomerization of vinyl chloride with methyl propionate

Conclusions The teloHierization of vinyl chloride with methyl propionate was accomplished and it was shown that telomers of type are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2537–2540, November, 1973.     

Nonempirical calculations of potential energy surfaces,structures, and stabilities of OF2Li+, SF2Li+, F2Li+, and CIFLi+ ions

Nonempirical calculations were carried out for the potential energy surfaces of OF₂Li⁺, SF₂Li⁺, F₂Li⁺, and ClFLi⁺ using the SCF/TEHD+P approximation. The stability of the bridged structure in comparison with the classical structure is enhanced upon replacement of the oxygen atom by sulfur and replacement of fluorine by chlorine. A bridged structure with Li–F–M and . bonds is the major form for all the fluorides examined. The classical structure LiMF _k ⁺, where Li is bound directly to the M atom, corresponds to an apex of a potential barrier and is either close or greater on an energy scale to the dissociation limit to Li⁺+MF _k . A comparison was made with analogous hydride complexes, which, in contrast to the fluorides, display isomerism.Institute of New Chemical Problems, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 6, pp. 19–22, November–December, 1989.     

Beitrag zur Kenntnis der Viskosezersetzung. Die Dissoziationskonstante der Cellulosexanthogensäure

Zusammenfassung Nachdem plausibel gemacht werden konnte, daß bei verschiedenen Zersetzungs- bzw. Regenerationsprozessen als Zwischenprodukt freie Cellulosexanthogensäure (CXS.) auftritt und dieselbe z. B. in vorliegender Arbeit im frisch gesponnenen Faden tatsächlich nachweisbar war, wurde auch versucht, die Dissoziationskonstante derselben abzuschätzen. Die dabei auftretenden Schwierigkeiten — sowohl hinsichtlich der experimentellen Durchführung wie auch die durch das Fehlen einer Theorie polyvalenter Makroionen — werden diskutiert. Aus mehreren unabhängigen Messungen, unter Bedachtnahme auf Ergebnisse an Celluloseglycolsäureäther vonKagawa undKatsuura, wird wahrscheinlich gemacht, daß die Dissoziationskonstante der verdünnten Säure zwischen 2,1 und 5,5·10^–5 liegt. Mithin ist die Cellulosexanthogensäure etwas stärker als Essigsäure, die im verdünnten Zustand bekanntlich Na-Cellulosexanthogenat ziemlich unzersetzt läßt^{2, 9, 12}.Abschließend wurde noch das Röntgendiagramm von präzipitiertem Na-Cellulosexanthogenat wiedergegeben.Mit 4 AbbildungenHerrn Prof. Dr.A. Skrabal zum 75. Geburtstag gewidmet.     

β-Substituted cyclopropyl rádicals grafted to silica surface. Methods of preparation,structure, and properties

Cyclopropyl type radicals were identified on a surface of activated silica by ESR. The possibility of their preparation by two methods,i.e., by photocyclization of substituted allyl radicals and by interaction of cyclopropane molecules with particular surface defects, was demonstrated. The effects of -substituents on radiospectroscopic characteristics and thermal stabilities of the radicals were studied. Rate constants and activation energies of decomposition of substituted cyclopropyl radicals were estimated. The experimental data obtained were compared with the results of quantum-chemical calculations of model systems. The mechanism of photocyclization of allyl radicals was discussed. The transition states of decomposition of cyclopropyl and -fluorine-substituted cyclopropyl radicals were calculated. Electronegative substitution was found to result in a considerable decrease in the activation energy of the cyclopropane ring opening.The authors are grateful to E. G. Baskir for calling their attention to this publication.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2409–2421, December, 1995.The work was carried out with financial support of the Russian Foundation for Basic Research (Project code 94-03-09137) and the International Science Foundation (Grant No. MK9000).     

Structure of products of the addition of methane- and ethane-sulfenyl chlorides to acrylic acid derivatives

Conclusions When alkanesulfenyl chlorides are added to acrylic derivatives CH₂=CHR (R=COOH, COOCH₃, COOCH₃ CN, CONH₂ a mixture of the isomers and is formed and the proportions of these depend on the nature of the substituent R.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1069–1075, June, 1966.     

Quantum-chemical study on the tautomerism of primary nitramines: the mechanism of N-nitro-anion protonation excludingaci-form formation

The values of the energy barriers to intramolecular 1,3-H shift reactions, in whichaci-forms of N- and C-nitro-compounds: 1 and are capable of transforming into 2 and , respectively, have been calculated by the semi-empirical AM1 method. The barrier heights (39 and 59.4 kcal/mol) reflect the kinetic stability of both tautomeric forms of the N- and C-nitro-compounds.Ab initio calculations in the 3–21G basis set of the structure and energies of stationary points on the potential energy surface of the system MeN=NO₂ H₃O demonstrated that there exists the principal possibility of the formation of only tautomer 2 (which is more stable than1).Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No 1, pp. 100–104, January, 1993.     

Replacement of carbon monoxide by π-ligands in fluorinated iron complex

Conclusions The -allylidene complex is formed in the photochemical reaction of with 1,3-butadiene and 1,3-cyclohexadiene, with subsequent replacement of the carbonyl group by the appropriate ligand.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2130–2131, September, 1977.