Synthesis of optically active analogs of α-tocopherol based on (S)-(+)-dihydromyrcene

New optically active analogs of α-tocopherol (vitamin E) were synthesized starting from enantiomerically enriched (ee≈50%) (S)-(+)-dihydromyrcene. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1631–1634, September, 2000.     

The effect of anions in the coordination spherè of Mg complexes ofN-acetyldehydrophenylalanyl-(S)-valine on the diastereoselectivity of hydrogenation

Diastereoselective hydrogenation in ethanol over Pd/C ofN-acetyldehydrophenylalanyl-(S)-valine (1) as complexes with Mg salts of strong acids gives predominantlyN-acetyl-(S)-phenylalanyl-(S)-valine (de up to 60%). In the case of complexes of1 with Mg salts of weak acids, the sign of asymmetric induction changes. Data of¹⁹F NMR spectroscopy ofN-acetyldehydro(p-fluorophenylalanyl)-(S)-valine indicate that in the former case, the anion of a strong acid does not enter the coordination sphere of the complex, whereas in the larter case, the anion of the weak acid does. The nature of the solvent also influences the reaction stereoselectivity. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1704–1706, September, 1999.     

Formation of Bessel light pulses by means of a conical mirror

The feasibility of forming diffractionless Bessel light pulses by means of a conical mirror is demonstrated. The dependence of the spatial-temporal and energy characteristics of these pulses on the mirror parameters is examined.     

Synthesis of complex sulfide phases on the CaYb<Subscript>2</Subscript>S<Subscript>4</Subscript>-Y<Subscript>2</Subscript>S<Subscript>3</Subscript> quasibinary section and investigation of their structural and electrolytic properties

The possibility of synthesizing sulfide-conducting solid electrolytes in the CaYb₂S₄-Y₂S₃ quasibinary system is tested for the first time. The system is characterized by the X-ray diffraction analysis and the electron microscopy. The total conductivity of specimens is found by the conductometric method. The ionic and electronic transport numbers are determined based on the modified versions of the emf method and the Hebb-Wagner polarization method. The possible mechanism of defect formation is discussed.     

Effect of the “inversion” of a scattering medium in layers of close-packed titanium dioxide nanoparticles

The features of the behavior of the diffuse transmission of layers of close-packed titanium dioxide nanoparticles in the visible and near infrared spectral ranges with an increase in the volume fraction f of the particles in a layer have been analyzed. It has been found that an increase in f for layers of small particles (about 25 nm) with a relatively low volume fraction (0.20–0.25) is accompanied by the expected decrease in diffuse transmission. At the same time, an increase in f for layers of large particles (about 100 nm) with a volume fraction of 0.45–0.50 results in a strong increase in transmission. The described phenomenon has been interpreted in terms of the concepts of inverse scattering systems, where the main scattering centers are air nanocavities in a TiO₂ matrix rather than TiO₂ particles in an air matrix.     

N-benzyl-N-[(E)-2-phenylethenyl]trifluoromethanesulfonamide

In the search for an approach to N-vinyltriflamides with a free NH group TfNHCH=CHR (Tf = CF₃SO₂) N-(benzyl)-N-(2-bromo-2-phenylethenyl)triflamide TfN(Bn)CH=CHPh was synthesized through bromination-dehydrobromination of N-(benzyl)-N-(2-phenylethyl)triflamide. At removing the benzyl protecttion by the action of trifluoromethanesulfonic acid benzyl alcohol separated; however instead of the target N-styryltriflamide unexpectedly the product of its hydrogenation was obtained, N-(2-phenylethyl)triflamide. Obviously, the benzyl alcohol was the hydrogen donor, and the easy hydrogenation was facilitated by the high electrophilicity of the double bond in N-styryltriflamide because of strong electron-acceptor effect of the triflyl group.