Kinetics of formation of a linear polymer-polymer network system in the presence of 3d metal chelates

For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation of the network and the linear polymer is preserved. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006.     

Quantum-chemical study of spectral and luminescent properties and photochemistry of polyatomic molecules

The potential of a package of quantum-chemical software programs for exploring physicochemical problems pertaining to polyatomic organic molecules is highlighted. The results of investigation into the spectral, luminescent, and photochemical properties of molecules are discussed. The necessity of development of target-oriented models for studying the problems of physics and chemistry of molecules is emphasized.     

The First Iminoamidophosphite Ligand: Synthesis and Complexation with Rhodium(I)

Optically active amidophosphite with the peripheral imino group (R)-(Et₂N)₂POCH₂CH(Et)N=CHPh is synthesized through one-stage phosphorylation of the corresponding imino alcohol. Its reaction with [Rh(CO)₂Cl]₂ (at P : Rh = 1) yields the mononuclear chelate [Rh(CO)(P^N)Cl]. Structures of the compounds are determined by IR, ³¹P, and ¹³C NMR spectroscopy, mass spectrometry, and polarimetry.     

Metabolites of the marine fungus <Emphasis Type="Italic">Humicola fuscoatra</Emphasis> KMM 4629

A new sesquiterpene of the caryophyllene series, fuscoatrol A (1), and known compounds, 11-epiterpestacin (2) and -nitropropionic acid (3), were isolated from the marine fungus Humicola fuscoatra (Traaen) KMM 4629 associated with the Kuril colonial ascidium. The structure of 1 was established on the basis of X-ray diffraction data and 2D NMR spectroscopy. The antimicrobial and cytotoxic activities of compounds 1–3 were studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2534–2537, November, 2004.     

Stereospecific synthesis of octaprenols WT3C4OH and WT3C3TOH

A total synthesis of the above prenols has been carried out.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2333–2338, October, 1991.     

Enantio- and Diastereoselective Aldol-Reaction of 2,6-Dimethylphenyl Propionate Using Titanium-Carbohydrate Complexes

Chloro(cyclopentadienyl)bis(1,2:5,6-di-O-isopropylidene-α-D -glucofuranos-3-O-yl)titanium ( 1 ) is used for the transmetallation of Li-enolates obtained from propionyl derivatives. While such Ti-enolates of ketones and hydrazones appear to be unreactive, the (E)enolate 13 of 2,6-dimethylphenyl propionate ( 11 ) adds to the re-side of aldehydes, affording various syn-aldols 14 with high dia- and enantioselectivity (92–97% ds, 91–97% ee, cf. Scheme 2 and Table 1). Racemic syn-aldols (±)- 14 are obtained analogously from the achiral bis(2-propyloxy)-Ti-enolate 15 (Scheme 2 and Table 2). In contrast to the unstable Li-enolate 10 , the Ti-enolates 13 and 15 isomerize at ?30°, presumably to the thermodynamically more stable (Z)-enolates (Scheme 4), While the diastereoselectivity of the achiral enolate 15 is lost upon this equilibration, the chiral (Z)-enolate 27 quite unexpectedly affords anti-aldols 12 of high optical purity (94–98% ec) and, in most cases, with acceptable-to-good diastereoselectivity (82–90% ds). Notable exceptions are branched unsaturated and aromatic aldehydes which form a greater proportion of synepimers of moderate optical purity (Scheme 5 and Table 3). Consistent with these findings, re-facial-and ami -selective aldol-addition is also exhibited by the (Z)-configurated Ti-enolate 22 of N-propionyl-oxazolidi-none 19 (Scheme 3).     

Kinetics of thermochemical pretreatment of lignocellulosic materials

The results of an experimental study of the acid hydrolysis of hardwood are presented in the form of values for the three parameters, activation energy, power on the acid concentration, and pre-exponen-tial factor, of the first order kinetic constants for each of the following reaction participants: xylan remaining, glucan remaining, xylose formed, and xylose decomposed. These are used as a base for a quantitative theory to predict the temperature, time, and acid concentrations needed for effective pretreatment of the substrate for subsequent enzymatic hydrolysis of the glucan. This theory is based on the assumption that successful pretreatment requires >90% removal of the xylan, <10% removal of the glucan, and >80% xylose yield. This theory is compared with selected published data.     

Boron chelates with 5,5,5-trifluoro- and 5,5,5-trichloro-4-aminopent-3-en-2-ones

Boron chelates were obtained by the reaction of butoxy(butylthio)diphenylborane with 5,5,5-trifluoro(trichloro)-4-aminopent-3-en-2-one, and their reactions with primary amines were investigated. -Diiminate complexes of boron with trifluoro- and trichloromethyl groups were synthesized.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2657–2661, November, 1992.     

The application of INAA to the geochemical analysis of single diamonds

Instrumental neutron activation analysis (INAA) has been applied to the analysis of 62 small (0.01–0.5 carat), single, inclusion-bearing and inclusion-free diamonds from South Africa, Brazil and Colorado. Up to 40 elements were detected at the ppb and ppt levels in individual diamonds of the eclogitic (basaltic affinity) and the peridotitic (ultramafic) paragenesis. The data obtained in this study can be used to distinguish between diamonds from the eclogitic and peridotitic parageneses and provides geochemical information on the environment in which diamonds crystallize. Further, the technique may prove to be useful in fingerprinting diamonds of different provenance areas.     

Synthesis of (trichloromethyl)organosilanes by catalytic decarboxylation of (trichloroacetoxy)organosilanes

A method for preparing (trichloromethyl)organosilanes by the catalytic decarboxylation of the corresponding trichloroacetoxysilanes RMe₂SiOC(O)CCl₃ (R = Me, ClCH₂, Ph, Me₃Si, and H) has been developed. The method involves heating the starting compounds without a solvent in the presence of a catalyst (quaternary ammonium salts or potassium salts with the addition of crown ethers). Tertiary amines (Et₃N, Bu₃N) catalyze this reaction only when heating is carried out in donor aprotic solvents (THF, acetonitrile) in the presence of oxygen. Thermal decomposition of (trichloroacetoxy)organosilanes, in contrast to catalytic decarboxylation, begins at a higher temperature and yields a mixture of products.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 150–153, January, 1995.