Reactions of trimethylsilyl fluorosulfonyldifluoroacetate with purine and pyrimidine nucleosides

Difluorocarbene, generated from trimethylsilyl fluorosulfonyldifluoroacetate (TFDA), reacts with the uridine and adenosine substrates preferentially at the enolizable amide moiety of the uracil ring and the 6-amino group of the purine ring. 2′,3′-Di-O-benzoyl-3′-deoxy-3′-methyleneuridine reacts with TFDA to produce 4-O-difluoromethyl product derived from an insertion of difluorocarbene into the 4-hydroxyl group of the enolizable uracil ring. Reaction of the difluorocarbene with the adenosine substrates having the unprotected 6-amino group in the purine ring produced the 6-N-difluoromethyl derivative, while reaction with 6-N-benzoyl protected adenosine analogues gave the difluoromethyl ether product derived from the insertion of difluorocarbene into the enol form of the 6-benzamido group. Treatment of the 6-N-phthaloyl protected adenosine analogues with TFDA resulted in the unexpected one-pot conversion of the imidazole ring of the purine into the corresponding N-difluoromethylthiourea derivatives. Treatment of the suitably protected pyrimidine and purine nucleosides bearing an exomethylene group at carbons 2′, 3′ or 4′ of the sugar rings with TFDA afforded the corresponding spirodifluorocyclopropyl analogues but in low yields.     

New Schiff base complexes of ruthenium(III) and their use as catalysts for O-allyl systems isomerization

Seven new ruthenium(III) complexes of the general formula [RuCl(PPh₃)LL′] · xH₂O (LL′ = [ONNO] = symmetrical and unsymmetrical Schiff base derivatives of trans-1,2-diaminocyclohexane and 2-hydroxynaphthaldehyde as well as R-salicylaldehydes, x = 0–3) have been synthesized. The complexes were characterized by physico-chemical and spectroscopic techniques. The catalytic activities of the complexes in the isomerization reaction of selected O-allyl systems, i.e., 1,4-diallyloxybutane and 4-allyloxybutan-1-ol have been studied. Some of the complexes showed high efficiency and E-stereoselectivity in double bond migration of allyl group to 1-propenyl group and high selectivity of isomerization of allyloxyalcohol to cyclic acetal.     

über die Dispersion von Luft und Kohlendioxyd in dem Wellenlängenintervall von 600 bis 60 m

Zeitschrift für Physik A Hadrons and nuclei - Die Änderung der Dielektrizitätskonstanten von Luft und Kohlendioxyd mit der Wellenlänge wurde in dem Intervall von 600 bis 60m...     

Spectroscopic investigations on polypropylene‐carbon nanofiber composites. I. Raman and electron spin resonance spectroscopy

Isotactic polypropylene‐vapor grown carbon nanofiber composites containing various fractions of carbon nanofibers, ranging from 0 to 20 wt %, have been prepared. Raman spectroscopy was used to analyze the effect of the dispersion of carbon nanofibers within polypropylene and the interactions between carbon nanofibers and macromolecular chains. The as‐recorded Raman spectra have been successfully fitted by a linear convolution of Lorentzian lines. Changes of the Raman lines parameters (position, intensity, width, and area) of polypropylene and carbon nanofibers were analyzed in detail. The Raman spectra of the polymeric matrix—at low concentrations of nanofibers—show important modifications that indicate strong interactions between carbon nanofibers and the polymeric matrix reflecting by vibrational dephasing of macromolecular chains. The Raman spectrum of carbon nanofibers is sensitive to the loading with carbon nanofibers, showing changes of the resonance frequencies, amplitudes, and width for both D‐ and G‐bands. Raman data reveals the increase of the disorder, as the concentration of carbon nanofibers is increased. The presence of the typical ESR line assigned to conducting electrons delocalized over carbon nanofibers is confirmed and the presence of a spurious magnetic line due to catalyst's residues is reported. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1644–1652, 2009     

Enantioselective route to 3-vinylidene tetrahydropyrans and 3-vinylidene oxepanes based on a silyl-Prins cyclization

A general method has been developed for the asymmetric synthesis of 3-vinylidene tetrahydropyrans and 3-vinylidene oxepanes based on the Lewis acid-catalyzed intramolecular reactions of oxocarbenium ions with propargylsilanes. The observed excellent diastereoselectivity and a high asymmetric induction offer a new synthetic method with a wide scope and generality.     

New thermoplastic poly(carbonate-urethane)s based on chain extenders with sulfur atoms

New thermoplastic segmented polyurethanes were obtained by a one-step melt polyaddition using 40, 50 and 60 mol% poly(hexane-1,6-diyl carbonate) diol of \(\bar{M}_{n} = 860\) g mol^?1, 1,1′-methanediylbis(4-isocyanatobenzene) and 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol, 2,2′-[oxybis(benzene-1,4-diylsulfanediyl)]diethanol or 2,2′-[sulfanediylbis(benzene-1,4-diylsulfanediyl)]diethanol as a chain extender. FTIR, atomic force microscopy, differential scanning calorimetry and thermogravimetry were used to examine the polyurethanes’ structure and thermal properties. Moreover, their Shore A/D hardness, tensile, adhesive and optical attributes were determined. They were transparent high-molar-mass materials showing good tensile strength (up to 51.9 MPa). The polyurethanes exhibited improved adhesion to copper taking into consideration that of conventional ones, and middle or high refractive index values (1.57–1.60), and both these parameters increased with an increase of the content of sulfur atoms in the polyurethane chain. The newly obtained polyurethanes can be considered as materials for numerous medical and optical appliances.     

Studies on the uptake of different arsenic forms and the influence of sample pretreatment on arsenic speciation in White mustard (Sinapis alba)

The concentration and speciation of arsenic incorporated by plants grown in the presence of different arsenic compounds was compared, and the influence of plant sample pretreatment and extraction procedures on the recovery and reliability of speciation analyses was studied. It was concluded that sample pretreatment greatly affected the extraction efficiency, but did not change arsenic speciation. The most suitable extraction procedure involved dried plant material without the use of liquid nitrogen. To assess the ability of White mustard to uptake arsenic in different forms, samples were cultivated in nutrient solutions containing either As(III), As(V), monomethylarsonic acid (MMA) or dimethylarsinic acid (DMA). The translocation factor was the highest (0.70) when DMA was added to the nutrient solution, however the overall As concentration in plant tissues was the lowest in this case. Only inorganic As was found in plant tissues when either As(III) or As(V) was added to the nutrient solution. When organic arsenic was present in the nutrient medium, however, it was partially transformed by the plants into inorganic forms.     

Isomerical and structural determination of N-hydroxyurea: a matrix isolation and theoretical study

The structure, isomerization pathways and vibrational spectra of the important N-hydroxyurea (HU) molecule were studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the MP2/6-311++G(2d,2p) level of theory. In agreement with theoretical predictions, 1Ea represents the most stable keto isomer in the gas-phase, being the dominant species trapped in argon matrices, while the 1Za isomer also contributes to the spectrum of isolated HU molecules. According to the calculated abundance values at the temperature of evaporation of the compound (393 K), the 1Ea and 1Za isomers together with a small contribution of 1Eb are expected to appear in the experimental spectra. Since the barrier for interconversion 1Ea? 1Eb is only ～2 kJ mol(-1), these two isomers are in equilibrium in the matrices and, at low temperature, the population of the less stable 1Eb form is too small to be observed. Full assignment of the observed spectra of N-hydroxyurea and its deuterium analogue was undertaken on the basis of comparison with theoretical data.     

Circular dichroism, optical rotation and absolute configuration of 2-cyclohexenone-cis-diol type phenol metabolites: redefining the role of substituents and 2-cyclohexenone conformation in electronic circular dichroism spectra

The absolute configurations of 2-cyclohexenone cis-diol metabolites resulting from the biotransformation of the corresponding phenols have been determined by comparison of their experimental and calculated circular dichroism spectra (TDDFT at the PCM/B2LYP/Aug-cc-pVTZ level), optical rotations (calculated at the PCM/B3LYP/Aug-cc-pVTZ level) and by stereochemical correlation. It is found that circular dichroism spectra and optical rotations of 2-cyclohexenone derivatives are strongly dependent on the ring conformation (M or P sofa S(5) or half-chair), enone non-planarity and the nature and positions of the hydroxy and alkyl substituents. The effect of non-planarity of the enone chromophore, including the distortion of the C=C bond, is determined for the model structures by TDDFT calculations at the PCM/B2LYP/6-311++G(2d,2p) level. Non-planarity of the C=C bond in the enone chromophore is commonly encountered in 2-cyclohexenone derivatives and it is a source of significant rotatory strength contribution to the electronic circular dichroism spectra. It is shown that the two lowest-energy transitions in acrolein and 2-cyclohexenone and its derivatives are n(C=O)-π(C=O)* and π(C=C)-π(C=O)*, as expected, while the shorter-wavelength (below 200 nm) transitions are of more complex nature. In 2-cyclohexenone and its alkyl derivatives it is predominantly a mixture of π(C=C)-π(C=C)* and π(C=C)-σ* transitions, whereas the presence of hydroxy substituent results in a dominant contribution due to the n(OH)-π(C=O)* transition. A generalized model for correlation of the CD spectra of 2-cyclohexenones with their structures is presented.