Condensation of all-cis-tetraphenylcyclotetrasiloxanetetraol in ammonia: new method for preparation of ladder-like polyphenylsilsesquioxanes

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Global Analysis of the Flows of Fluids with Pressure-Dependent Viscosities

 To describe the flows of fluids over a wide range of pressures, it is necessary to take into account the fact that the viscosity of the fluid depends on the pressure. That the viscosity depends on the pressure has been verified by numerous careful experiments. While the existence of solutions local-in-time to the equations governing the flows of such fluids are available for small, special data and rather unrealistic dependence of the viscosity on the pressure, no global existence results are in place. Our interest here is to establish the existence of weak solutions for spatially periodic three-dimensional flows that are global in time, for a large class of physically meaningful viscosity-pressure relationships. (Accepted May 1, 2002) Published online November 15, 2002 Communicated by S. S. ANTMAN     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

New carbazole-containing polyphenylquinoxalines: Synthesis,photophysical, and electroluminescent properties

New carbazole-containing polyphenylquinoxalines combining the electron-transport behavior of quinoxaline with hole-transport and electroluminescent properties of carbazole have been synthesized. The polymers show solubility in organic solvents. Their glass transition temperatures range from 315 to 370°C, and temperatures corresponding to 10% weight loss vary from 510 to 560°C (in air). It has been demonstrated that these polymers exhibit electroluminescent behavior in the 450–750 nm spectral region and offer promise as emitting and electron-hole transport materials for polymeric light-emitting diodes.     

Synthesis of amorphous block copoly(arylene ether ketones) and their characterization

Exchange reactions that may proceed in the course of polycondensation during formation of a polymer from 4,4′-difluorobenzophenone and 4,4′-(isopropylidene)diphenol have been studied. It has been shown that the molecular mass of the polymer decreases under the action of 4,4′-(isopropylidene)diphenol diphenolate. The nucleophilic substitution of the activated aryl halide in DMAA in the presence of potassium carbonate yields high-molecular-mass block copoly(arylene ether ketones) based on 4,4′-difluorobenzophenone and a number of bisphenols. It was demonstrated the synthetic procedure and the chemical structure of block copoly(arylene ether ketones) strongly affect the onset temperature of softening and the mechanical characteristics of the films based on these polymers.     

Product structure in the reaction of dimethyl acetylenedicarboxylate with 2-furyl-1,2,3,4-tetrahydroquinolines

Dimethyl acetylenedicarboxylate reacts with 4-substituted and 3,4-fused 2-furyl-1,2,3,4-tetrahydroquinoline derivatives at the furan fragment according to the [4 + 2]-cycloaddition pattern. The reaction is not stereoselective, and it yields two diastereoisomeric 7-oxabicyclo[2.2.1]hepta-2,5-dienes whose structure was determined by X-ray analysis and NMR spectroscopy.     

Effect of aryl ligands on the chemical hardness of arylmercury cations

¹⁹F NMR spectroscopy was used to study the exchange reactions involving 4-fluorothiophenoxides, 4-nitrophenoxides, chlorides, and acetates of arylmercury and triphenylphosphinegold. The analysis of the data on equilibrium constants allows one to obtain information on the comparative chemical hardness of ArHg⁺ and Ph₃PAu⁺ cations. The increase in the electron-donating ability of aryl ligands enhances the chemical hardness of ArHg⁺ cations, their influence being best described by ⁰ constants of substituted phenyl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1255–1260, May, 1996.     

Aryl-bis(triorganylphosphine)nickel phenoxides

Compounds of general formulatrans-ArNi(PR₃)₂OAr' (R = Et, cyclohexyl; Ar = 2-MeC₆H₄, 2-FC₆H₄; Ar' = 4-FC₆H₄, 4-NO₂C₆H₄) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR₃)₂Cl with TlBF₄. Syntheses of 4-fluorophenoxide complexes, ArNi(PR₃)₂OC₆H₄F-4, additionally give some quantities oftrans-[ArNi(PR₃)₂OC₆H₄F-4][HOC₆H₄F-4] adducts. Exchange reactions MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4 + XC₆H₄OH 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄X + 4-FC₆H₄OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK _eq and pK _a of XC₆H₄OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995.     

The study of coordinative interaction in the organoaluminium derivatives of substituted phenols

Intramolecular coordination in dimethylaluminium phenoxides (with an ortho-substituted ring) was investigated. Only strongly donating groups in the phenoxy ring (COOMe) displayed strong intramolecular coordination. All compounds investigated formed donor-acceptor complexes with hexamethylphosphoramide (HMPA). Dimethylaluminium methylsalicilate coordinated HMPA without splitting the intramolecular carbonyl oxygen—aluminium bond, which suggests formation of the pentacoordinated aluminium atom.