Synthesis of 2-substituted isoxazoline and imidazoline,containing a vinylacetyl fragment

The reaction of4-dialkylamino-1-acetyl-1-buten-3-ynes with 1-hydroxy-2-aminoethane and 1,2-diaminoethane was used to synthesize 2-substituted oxazoline and imidazoline, containing a fully enolized vinylacetyl fragment.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1409–1410, October 1992.     

Synthesis of oligosaccharide fragments of the Streptococcus pneumoniae type 14 capsular polysaccharide and their neoglycoconjugates with bovine serum albumin

2-Aminoethyl glycosides of tetra-, hexa- and octasaccharide fragments of the bacteria Streptococcus pneumoniae type 14 capsular polysaccharide were synthesized within a project directed to the development of pneumococcal conjugated vaccine based on synthetic carbohydrate ligands. Squarate method was used to obtain neoglycoconjugates of the synthesized oligosaccharides with bovine serum albumin.     

Titanium(4+) and zirconium(4+) dichloride complexes with pyridinedicarboxylic acid derivatives as ethylene polymerization catalysts

Titanium(4+) and zirconium(4+) complexes with pyridinedicarboxylic acid derivatives have been synthesized. The composition and structure of the synthesized 2,6-bis(diphenylhydroxymethyl)pyridine complexes have been corroborated by NMR and IR spectroscopy, and elemental analysis. The complexes activated with methylaluminoxane (MAO) are catalytically active in ethylene polymerization, Depending on the Ti/Al_MAO ratio, the catalytic activity of the complexes varies between 90 and 420 kg PE/mol Ti h atm.     

Maximally movable spaces of Finsler type and their generalization

In this paper, we consider some generalization of maximally movable spaces of Finsler type. Among them, there are locally conic spaces (Riemannian metrics of their tangent spaces are realized on circular cones) and generalized Lagrange spaces with Tamm metrics (their tangent Riemannian spaces admit all rotations). On the tangent bundle of a Riemannian manifold, we study a special class of almost product metrics, generated Tamm metric. This class contains Sasaki metric and Cheeger–Gromol metric. We determine the position of this class in the Naveira classification of Riemannian almost product metrics.     

Oxidation of bis(Trimethylsilyl)amidodifluorophosphite

Conclusions The reaction of tert-butyl hypochlorite with bis(trimethylsilyl)amidodifluorophosphite gives an intermediate quasiphosphonium salt, which decomposes losing either the trimethylsilyl group or tert-butyl group with equal probability.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1426–1428, June, 1989.     

Synthesis and properties of super high molecular weight polyhexene-1

TiCl₄–alkylaluminium systems have been fixed on graphite and other inorganic supports and used in hexene-1 polymerization. Kinetic studies show a decreasing polymerization rate from high initial values. High conversions (up to 99%) are reached, although retardation by a diffusion process is observed above 60%. The polymers have high molecular weights (up to 10⁷) and high isotacticity (up to 98.5% from ¹³C NMR analysis). The effects of the nature of the components (carrier, alkylaluminium), and their concentration on the polymerization kinetics and the molecular structure of the polymer are discussed. The linear chain has one alkyl group (the alkylaluminium) and one unsaturation as the chain ends. Despite the high tacticity, the polymers are amorphous and rubber-like.     

Triisobutylaluminum as cocatalyst for zirconocenes. I. Sterically opened zirconocene/triisobutylaluminum/perfluorophenylborate as highly effective ternary catalytic system for synthesis of low molecular weight polyethylenes

Ethylene polymerizations with catalytic systems Me₂SiCp*N^tBuZrX₂ ( 1 ) [Cp* = C₅(CH₃)₄; X = Cl ( 1Cl ), Me ( 1Me )], triisobutylaluminum (TIBA), perfluorophenylborate CatB(C₆F₅)₄ [Cat = CPh₃ ( 3 ), Me₂NHPh ( 4 )], or Me₂SiCp₂ZrX₂ [X = Cl ( 2Cl ), Me ( 2Me )]/TIBA/ 3 ( 4 ) were performed within a wide range of ethylene pressures of different Al/Zr ratios, and Zr/B = 1. Catalytic systems 1Cl ( 2Cl )/TIBA/ 3 led to the formation of very high linear molecular weight polyethylene (PE) of M_η ∼2,000,000 with low activity. The replacement of both chlorine ligands in the precatalyst for the methyl ones led to the formation of active species producing low molecular weight PE with high activity. Chain transfer to ethylene was shown to be the main reaction controlling PE chain propagation: k_p/k_tr ∼20–30 for 1Me /TIBA/ 3 and k_p/k_tr ∼350–500 for 2Me /TIBA/ 3 . It was suggested that TIBA was present in the active center first in the form of a neutral heterobimetallic Zr–Al bridged complex followed by the formation of a partially polarized Zr–Al(Cl)R₂ (R = ⁱBu) or an unreactive Zr–AlR₃ cationic complex by abstraction of the alkyl ligand under the action of borate. It was concluded that AlR₃ from the latter cationic complex may be easily reversibly replaced under the specific coordination of ethylene or accumulated α-olefin, giving rise to highly labile and sterically accessible cationic species. Experiments on ethylene polymerization with the catalytic systems 1Cl ( 1Me )/TIBA/ 3 /Ph₂NH, 1Cl ( 1Me )/TIBA/ 4, 2Cl ( 2Me )/TIBA/ 3 /Ph₂NH, and 2Cl ( 2Me )/TIBA/ 4 were performed to confirm the suggestion. Catalytic systems derived from dichloride complexes in the presence of a σ-donor substrate also produced low molecular weight PEs with molecular weight characteristics similar to those of products obtained with the dimethylated precatalysts. The specific feature of active species derived from 2Me complexes to isomerize coordinated α-olefin into trans-vinylene polymer chains was also revealed. The catalytic behavior of the ternary catalytic system based on 2Me relative to 2Me or 2Cl precatalysts activated with polymethylaluminoxane at different Al/Zr ratios was compared. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1901–1914, 2001