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51.
James P. Kutney Peter Grice Krystyna Piotrowska Steven J. Rettig Jerzy Szykula James Trotter Loc Van Chu 《Helvetica chimica acta》1983,66(6):1820-1826
The thujone-derived enone 1 , upon base-catalyzed reaction with 2-methyl-6-vinylpyridine is converted to the pyridine analogue 5 (Scheme 1). Catalytic reduction of the latter to 6 generates two new centers of chirality which eventually become C(8) and C(14) in the ultimate synthetic steroid analogue 12 . An X-ray analysis of 6 establishes the structure and absolute configuration so as to determine its suitability in subsequent synthetic studies. The acetal derivative 7 , via Birch reduction, hydrolysis, and internal aldol cyclization, is converted into the cyclohexenone analogue 10 (Scheme 2). This ‘one-pot’ process affords an efficient conversion of the pyridine ring into a cyclohexenone system required for A-ring construction of the steroid skeleton. Finally, conversion of 10 , via the unsaturated diketone 11 , provides the chiral steroid analogue 12 . 相似文献
52.
Jerzy Walendziewski 《Reaction Kinetics and Catalysis Letters》1991,43(1):107-113
Porous structure, acidity and hds activity of the CoMo–P–Al2O3 catalysts have been studied. Phosphorus was introduced jointly with molybdenum. This method of phosphorus incorporation gave substantial diminution of surface area, moderate changes of acidity and decrease in hds activity for the catalysts with P2O5 content higher than 5 wt.%.
, CoMo–P–Al2O3. . , P2O5 5 .%.相似文献
53.
Sławomir J. Grabowski Andrzej J. Sadlej W. Andrzej Sokalski Jerzy Leszczynski 《Chemical physics》2006
The F3CCl?FH and F3CCl?FCH3 dimers, which feature the halogen–halogen contacts, are investigated at MP2/6–311++G(d,p) and MP2/aug–cc–pVDZ levels of approximation. The binding energies of these complexes are found to be comparable to those of the weak hydrogen bonds. In both complexes the Cl?F are found to be significantly shorter than the sum of the corresponding van der Waals radii. The C–Cl?F contacts are also found to exhibit certain deviation from linearity. However, the energy differences between linear and bent structures are very small and primarily accounted for by electrostatic interactions between remote parts of the dimer. This indicates a high conformational flexibility of the halogen–halogen contacts and may help to explain the diversity of structural features in crystals formed by halogen-containing molecules. In both dimers the halogen–halogen interaction leads to certain shortening of the C–Cl electron accepting bond. This is accompanied by a small increase of the C–Cl stretching frequency. Hence, the two investigated dimers can possibly be classified as the blue-shifting halogen–halogen contacts. 相似文献
54.
Supermolecular interaction energies are analyzed in terms of the symmetry-adapted perturbation theory and operators defining the inaccuracy of the monomer wave functions. The basis set truncation effects are shown to be of first order in the monomer inaccuracy operators. On the contrary, the usual counterpoise correction schemes are of second order in these operators. Recognition of this difference is used to suggest an approach to corrections for basis-set truncation effects. Also earlier claims--that dimer-centered basis sets may lead to interaction energies free of basis-set superposition effects--are shown to be misleading. According to the present study the basis-set truncation contributions, evaluated by means of the symmetry-adapted perturbation theory with monomer-centered basis sets, provide physically and mathematically justified corrections to supermolecular results for interaction energies. 相似文献
55.
Agnieszka Bajorek Marcin Ciepluch Jerzy Pczkowski 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3481-3488
The series of 9‐acridyl derivatives of aromatic amines have been investigated as fluorescent probes for monitoring the progress of free‐radical polymerization. This study on the changes in the fluorescence intensity and spectroscopic shift of specific compounds was carried out during thermally initiated polymerization of methyl methacrylate and photoinitiated polymerization of 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate‐1‐methyl‐2‐pyrrolidonone mixture. The purpose of this investigation was to find a relationship between the changes in the shape and intensity of fluorescent probes and the degree of monomer conversion into a polymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3481–3488, 2002 相似文献
56.
B. Skwarzec D. I. Strumińska A. Boryło J. Falandysz 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(3):661-663
238U, 234U and 210Po activity concentrations were determined in beer in Poland by alpha-spectrometry with low-level activity silicon detectors.
The results revealed that the mean concentrations of 238U, 234U and 210Po in the analyzed beer samples were 4.63, 4.11 and 4.94 mBq·dm−3, respectively, the highest in Tyskie (5.71 for 210Po, 5.06 for 234U and 6.11 for 238U) and the lowest in Lech (2.49 for 210Po). The effective radiation dose due to uranium and polonium ingestions by beer was calculated and were compared to the effective
radiation dose from drinking water.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
57.
Jerzy Majnusz Robert W. Lenz 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2775-2788
A series of low molecular weight, thermotropic poly(2-alkyl-1,4-phenylene terephthalate)s was prepared by the solution polycondensation reaction of terephthaloyl chloride and alkylhydroquinones containing n-alkyl substituents of increasing size from methyl to dodecyl. Samples of the low molecular weight polymers so obtained were also further polycondensed in the solid state to obtain high molecular weight polymers. The liquid crystalline phase behaviors and textures were determined, and the effects of polymer structure and molecular weight on these properties are discussed. All of the polymers obtained formed thermotropic, nematic mesophases, which were less stable for the lower molecular weight polymers, as expected, than were the mesophases formed by the higher molecular weight polymers. © 1994 John Wiley & Sons, Inc. 相似文献
58.
Four 9H and four 7H tautomers of DNA base xanthine were studied by the ab initio LCAO-MO method at the MP2/6-311G**//HF/6-31G** and MP2/6-31G**//HF/6-31G** approximations. All calculated structures are minima at the HF/6-31G** potential energy surface with the dioxo 7H tautomer (A1) being the global minimum. The second most stable tautomer, dioxo-9H (B1) is by 9 kcal/mol less stable. For the A1 B1 transition the calculated MP2 energy gap corresponds to the equilibrium constant of 2 × 10–7. Therefore, only the major tautomeric form A1 is predicted to be detectable in the gas phase. The 7H and 9H groups of tautomers are discussed separately. Within both groups, the dioxo form (A1-7H, B1-9H) is the most stable one and is succeeded by the 2-dihydroxy (A2, B2) form. However, while the energy difference between A1 and A2 is 10 kcal/mol, the energy difference between B1 a B2 is only 2 kcal/mol. The effect of polar environment was estimated by the SCRF method, using a spherical cavity, at the HF/6-31G** level. These calculations did not change the gas phase stability order of the tautomers. However, the energy difference between A1 and B1 decreased from 9 kcal/mol at the HF/6-31G** level to 4 kcal/mol at the SCRF HF/6-31G** level. 相似文献
59.
Marian Miko?ajczyk Jerzy A. Krysiak Wanda H. Midura Micha?W. Wieczorek Jaros?aw B?aszczyk 《Tetrahedron: Asymmetry》1996,7(12):3513-3520
A general and efficient synthesis of enantiomeric α-chlorovinyl p-tolyl sulfoxides 1 using (+)-(S)C(S)S-α-chloro-α-dimethoxyphosphorylmethyl p-tolyl sulfoxide as a key substrate for the Horner-Wittig reaction with carbonyl compounds is described. The ratio of geometrical isomers of 1 was determined and briefly investigated. The X-ray diffraction structures of (Z)-1-chloro-1-p-tolylsulfinyl-2-phenyl-ethene and (Z)-1-chloro-1-p-tolylsulfinyl-2-(2-thienyl)-ethene are reported. 相似文献
60.
Dieter Seebach Albert K. Beck Jerzy Goliski John N. Hay Thomas Laube 《Helvetica chimica acta》1985,68(1):162-172
On the Steric Course of the Reaction of Enamines Derived from Open-Chain Aldehydes and Ketones with Nitro-olefins Yielding 2,3-Disubstituted 4-Nitroketones The relative configuration of the nitro-ketone 12 obtained by the title reaction has been proved by a Baeyer-Villiger degradation and subsequent reduction to the amino-alcohol (±)-(u)- 20 , the relative configuration of which is identical with a sample prepared from 2-methyl-3-hydroxybutyrate of known configuration (Scheme 1). The stereochemical course of the title reaction is thus as predicted by our topological rule. It is assumed that the other nitro-ketones 13–18 described here are also formed by (lk)-combination of the trigonal centers of the educts (diastereoselectivity > 90%, see Formulae and Fig. 1). It is not possible to reverse this relative topicity by employing (Z)- instead of (E)-components of the starting materials, due to the reversibility of the primary step of these Michael additions (Schemes 2 and 3, and Fig. 2). 相似文献