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).     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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).     

Synthesis of α-amino ketones

Summary A new method is described for synthesizing aromatic -amino ketones with the general formula , which is based on the condensation of azlactones with benzene in the presence of aluminum chloride.     

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.     

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.     

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.     

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.     

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.     

Interpolation of parameters of solutions expressed as functions of composition

The number of parameters in the polynomial is discussed for N components and a polynomial extending up to power n. This number is found to be but may be N less for relative thermodynamic functions. The equation of degree n for an N-component system requires the use of data for each of the i-component systems. Data on the n-component systems suffice if n相似文献   

Vibrational spectra and structure of sulfonium nitroimides

Vibrational spectroscopy and x-ray structure analysis have been used to investigate three new types of sulfonium nitroimides: N-nitrosulfylimides, N-nitrosulfoximides, and N,N-dinitrosulfodiimides. Structural parameters have been determined for the molecules , , and .Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2489–2496, November, 1991.     

Triterpene glycosides ofHerniaria glabra. I

Conclusions FromHerniaria glabra L. two triterpene glycosides, glabrosides B and C, have been isolated. We have shown that the first is the -D-glucopyranosyl-(16)--D-glucopyranoside, and the second is the Khimiya Prirodnykh Soedinenii, Vol. 6, No. 3, pp. 307–311, 1970     

Electronic and spatial structures of some derivatives of 5-phosphoranylidenbarbituric and 5-phosphoranylidenthiobarbituric acids

The spatial and electronic structures of some derivatives of 5-phosphoranylidenbarbituric and 5-phosphoranylidenthiobarbituric acids are investigated within the framework of the semiempirical MNDO approximation. The effect of the substituents at the phosphorus and nitrogen atoms on the geometry and distribution of electron density in the studied molecules is considered. Their pseudoaromatic -system, which is formed by diffuse lone electron pairs of the ion and two N atoms, involves alternating donor and acceptor centers. The pseudoaromatic fragment in these molecules is nearly planar, and the deviations from planarity are dependent on the size of the substituents at the phosphorus and nitrogen atoms.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1029–1034, June, 1995.