Preparation of polyfluorinated cycloalk-1-enyl-, alk-1-enyl-, and alkyliodine tetrafluorides using XeF2 in the presence of appropriate Lewis acids as fluorooxidant

Previously unknown polyfluorocyclohexenyl, and acyclic perfluoroalkenyliodine tetrafluorides were prepared in high yields. Perfluorocyclohex-1-enyliodine tetrafluoride was obtained from pentafluoroiodobenzene using XeF₂-NbF₅ in aHF. The reaction of C₆F₅I with the weaker fluorooxidant XeF₂-BF₃ in 1,1,1,3,3-pentafluorobutane (PFB) yielded C₆F₅IF₂, perfluorocyclohexa-1,4-dienyliodine difluoride, C₆F₅IF₄, perfluorocyclohexa-1,4, and 1,3-dienyliodine tetrafluoride as intermediate products on parallel reaction routes. Both perfluoroalkenyl iodides, cis- and trans-(CF₃)₂CFCFCFI, reacted with XeF₂-BF₃ in PFB to give the corresponding perfluoroalkenyliodine tetrafluorides, cis- and trans-(CF₃)₂CFCFCFIF₄. Even perfluoroalkyl iodides can be fluorinated by this reagent as was demonstrated by the preparation of C₆F₁₃IF₄ from C₆F₁₃I. Generally, the CFCIF_n fragment (n = 0, 2, or 4) in cyclic or acyclic perfluoroalkenyliodine compounds R_FIF_n did not undergo a transformation to the corresponding perfluoroalkyliodine compound. Furthermore, no perfluoroorganoiodine hexafluorides were detected in reactions with the fluorooxidant XeF₂-aHF or BF₃ or NbF₅.     

Cationic polyelectrolytes. III. Nitrile-group reaction of macromolecular compounds with N,N-dialkylaminoalkylamines

The chemical reaction in aqueous medium of polyacrylonitrile and acrylonitrile–vinyl acetate co-polymer using asymmetrical diamines of H₂N? (CH₂)_m? NR₂ (m = 2,3) structure was studied. It was found that the nitrile group is modified to an dialkylaminoalkylacrylamide group; also determined were the reaction conditions required to obtain the highest degree of chemical transformation of the nitrile groups. All modified compounds were characterized by analytical spectroscopy (IR and ¹H NMR) and by rheological methods. It was also established that glutaronitrile can be used as a low-molecular-weight model to study the chemical transformation of nitrile groups in polyacrylonitrile and related polymers.     

Cationic polyelectrolytes. II. Amination of chloromethylated polystyrene with hydroxyalkylic secondary amines

The reaction of chloromethylated polystyrene with methyl(2- hydroxyethyl)amine and butyle (2-hydroxyethyl)amine was studied kinetically. The reaction of benzyl chloride with these amines was also investigated for comparison. N,N-dimethylformamide and dioxane were used as solvents. The reactions of benzyl chloride with the two amines in these solvents took place according to normal kinetics of the second order. Reaction kinetics depend on the nature of the amine and solvent in Chloromethylated polystyrene reactions. In dioxane the self-accelerating effect of the reaction for β ? 0.5 is apparent. Steric hindrance of the reaction, beginning with a conversion degree of about 75%, wss observed for butyl(2-hydroxyethyl)amine in N,N-dimethylformamide. This self-accelerating effect is observed in dioxane at the same reaction degree. The activation energies and frequency factors were calculated for the amination of benzyl chloride and chloromethylated polystyrene with the two amines in N,N-dimethylformamide and dioxane.     

Etude sur le comportement thermique de quelques polymeres ignifugeants contenant du phosphore et des halogenes

The thermal behaviour a series of polyphosphonates was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The obtained data permitted the calculation of activation energies and reaction orders on decomposition zones by the Coats — Redfern method.     

C-I stretching vibrations in iodobenzenes

Comparison of the calculated and experimental IR and Raman spectra of a series of iodobenzenes showed that the C-I stretching vibrations for these compounds correspond to a very highly polarized Raman band at 150–270 cm^–1 (=0.1). The position of this band depends on the mass of the para substituent and relative position of the fluorine and iodine atoms in the molecule. The UV absorption spectral data indicate an interaction of the iodine atom and para substituents through the -system. Opposite substituent effects on the change in intensity of the B-band in the UV spectra of iodobenzenes and tetrafluoroiodobenzenes were noted.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2637–2639, November, 1991.     

Hydrogenating properties of complex rhenidm(VLI) oxides with perovskite structure

Conclusions Rhenium oxides with perovskite structure of the general formula where B^III=Y and Sm, and Ba₃LaZnReWO₁₂ containing Re(VII), exhibit catalytic activity in hydrogenation of ethyl acetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1236–1238, June, 1986.     

PageRank model of opinion formation on social networks

We propose the PageRank model of opinion formation and investigate its rich properties on real directed networks of the Universities of Cambridge and Oxford, LiveJournal, and Twitter. In this model, the opinion formation of linked electors is weighted with their PageRank probability. Such a probability is used by the Google search engine for ranking of web pages. We find that the society elite, corresponding to the top PageRank nodes, can impose its opinion on a significant fraction of the society. However, for a homogeneous distribution of two opinions, there exists a bistability range of opinions which depends on a conformist parameter characterizing the opinion formation. We find that the LiveJournal and Twitter networks have a stronger tendency to a totalitarian opinion formation than the university networks. We also analyze the Sznajd model generalized for scale-free networks with the weighted PageRank vote of electors.     

Time evolution of Wikipedia network ranking

X-ray circular magnetic dichroism, polarized neutron diffraction, ac susceptibility, and Seebeck effect have been measured for several members of the RCo₂ series (R = Ho, Tm, Er) as a function of temperature and applied magnetic field. The experimental results show robust parimagnetism (a general behaviour along the RCo₂ series with R being a heavy rare earth ion) and two reversal temperatures in some systems, which is an unexpected result. Polarised neutron diffraction show differences between results obtained on single crystals or polycrystalline ingots. We propose an interpretation of parimagnetic RCo₂ as a Griffiths phase of the high temperature, magnetically ordered, amorphous RCo₂ phase.