Phosphorylation of lignins I. Phosphorylation of piperidinomethylated dioxane lignin from cottonseed husks

The phosphorylation of piperidinomethylated dioxane lignin has been studied. It has been shown that the reaction takes place with the formation of quaternary ammonium phosphates, while the transesterification of dimethyl phosphite with an aliphatic hydroxy group of the lignin is also possible.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 275–277, March–April, 1993.     

Structural equilibrium (S=0) ⇄ (S=1)and inversion of the configuration of the seven-membered saturated metal-containing ring in four-coordinate pyrazolealdiminate metal chelates of nickel(II) based on tetradentate ligands

¹H and¹³C NMR, x-ray structural analysis, and magnetic moment measurements have shown that in 5-thio(seleno)pyrazolealdiminate complexes of nickel(II) based on tetradentate ligands containing the fragment, with n=2, flattening of the chelate unit takes place in solution and in the solid state. A similar structure in which the diamine metal-containing ring has the twist-chair conformation is observed for the crystals of the complexes with n=4. For the complexes with n=4 in solution at a temperature below –50°C, rapid (on the NMR time scale) interconversion of the flattened (P) (S=0) and pseudotetrahedral (T) (S=1) structures is observed, not accompanied by inversion of the tetrahedral configuration of the metal atom. At temperatures above –50°C, in addition to the low-barrier reactions (T) (P), conversion of the seven-membered saturated metal-containing ring and inversion of the tetrahedral configuration of the Ni atom with activation barriers of 48–51 kJ/mole are observed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 327–335, February, 1990.     

Study of the structure of poly(methyl methacrylate) obtained in the presence of potassium hydride

Electrospray ionization mass spectrometry (ESI-MS) in positive- and negative-ion mode and multi-step tandem mass spectrometry (ESI-MS ( n) ) were selected for the determination of the structure of poly(methyl methacrylate) obtained using potassium hydride as initiator. Macromolecules with methoxy and methyl starting groups, i. e. those situated at the beginning of the polymer backbone, were observed in this case. No other differences in the chain structure were found in the polymer.     

133Xe release during post-irradiation annealing of uranium metal in the presence of a constant volume of air

The fractional release of¹³³Xe at different temperatures was studied as a function of time in the presence of an atmosphere of air during post-irradiation annealing of uranium metal. It was found that the relation between the fractional release and t^1/2 is irregular. There is an initial step in the annealing curves (at the temperature range of 400–710°C) which decreases by increasing temperature and totally disappears at the high temperature of 800–1000 °C. The other parts of the release curves are typical for¹³³Xe release from uranium metal. The initial step was found to be due to the surface oxidation of uranium metal.     

Adsorptionsmodifizierung der oberfläche von mineralischen polymerfüllstoffen als die methode deren aktivierung

The process of modifying the surface of particles of dispersed polymer fillers, using tensides, has been studied. The main principles were established with regard to the effect of modification of titanium dioxide and kaolin on the structure formation in solutions and block formations of chlorinated poly(vinyl chloride) resin and rubber, depending on the nature and concentration of the modifier. The decisive part played by chemisorption of the tenside in lyophilization (water-repellency treatment) of the surface of the filler and its activation, as a structure former, has been elucidated.     

Inter-ring rotational potential of biphenyl and its effect on poly(p-phenylene)

Detailed ab initio studies have been done on the inter-ring torsional states of the biphenyl molecule using self-consistent field molecular orbital method. The potential goes through a minimum at an angle of 38°. The height of the potential barrier for the coplanar state is 2.01 kcal/mol. When the phenyl rings are perpendicular to each other, this height increases to 2.37 kcal/mol. The role of correlation and polarization is found to be important. The shape of the potential suggests that polyparaphenylene may possibly exist as a super helix.     

Gallium-, Indium-Mangan- und Thallium-Rhenium-Carbonylverbindungen

Gallium-, Indium-Manganese-, and Thallium-Rhenium Carbonyl Compounds Compounds of type Na{Cl_4?nM[Mn(CO)₅]_n} (M ? Ga, In; n = 1, 2, 3) were prepared by reaction of the Lewis acids MCl₃ and NaMn(CO)₅. Instead of the sodium salts were obtained the compounds (C₃H₇CO₂)₂InMn(CO)₄L (Indium atom with the coordination number 5) from Indium(III) butyrate with two carboxylate groups bonded as chelate ligands and NaMn(CO)₄L [L ? CO, P(C₆H₅)₃] in the molar ratio 1:1. By reacting TlCl with NaRe(CO)₅ i.r. spectroscopic measurements of the solution pointed out the intermediate product TlRe(CO)₅, which was unstable against a disproportionation reaction into Tl and Tl[Re(CO)₅]₃. The last named compound delivered as a thermal decomposition product Re₂(CO)₈[μ-TlRe(CO)₅]₂. I.r. bands of the new compounds were assigned.     

Cyclization of n-alkylazinium cations with bisnucleophiles. 4. Regio- and stereospecificity of the reactions of β-diketones with quinoxalinium salts and their aza and benzo analogs

The reactions of substituted quinoxalinium, benzo[g]- and benzo[f]quinoxalinium, and pyrido[2,3-b]pyrazinium salts with anions of -dicarbonyl compounds give furo[2,3-b]-annelated systems with strictly determined regio- and stereoorientations.See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1543–1548, November, 1981.     

Investigations of aromatic polyesters with polynaphthalene systems in the main chain—VI: NMR studies of the structure of the aromatic copolyesters

Nuclear magnetic resonance spectra of several kinds of terephthalic copolyesters of 4,4′dihydroxydinaphthyl 1,1′ and 2,2 bis(4-hydroxyphenyl) propane were recorded. Proton signals of the terephthalic acid unit corresponding to heterolinkages and homolinkages could be observed in the range from 8.23 to 8.53 ppm. The average sequence lengths and the degrees of randomness in the copolyesters were calculated from the intensities of these signals.     

Conformational effects in 3-halotetrahydropyrans

The conformational equilibria of 3-chloro- and 3-bromotetrahydropyran were measured by NMR and IR spectroscopy using model 2-alkyl-5-halotetrahydropyrans. The 3-chloro compound was 76·2% equatorial in carbon tetrachloride and 58·5% in acetonitrile and the 3-bromo compound 85% equatorial in carbon tetrachloride. The conformational equilibrium is discussed in terms of dipole, electronic and van der Waals effects.