A comparison of microwave-accelerated and conventionally heated iodination reactions of some arenes and heteroarenes, using ortho-periodic acid as the oxidant

A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method.     

Theory of electronic transport in two-dimensional systems in the presence of magnetic fields

Three parts of the paper [Czech. J. Phys.41 (1991) 620,7 are focused on the Landauer-Büttiker approach to the study of transport in two-dimensional electron systems, with particular attention to the influence of an external magnetic field. In the previous parts the Landauer formalism was generalized for two-dimensional systems in quantizing magnetic fields. In the present part we applied the formalism to an analysis of magnetoresistance measurements. The two-dimensional electron gas preserved in the non-dissipative quantum Hall regime acts as the ideal leads necessary in the Landauer-Büttiker approach. The voltage, applied to the gate, forms a scattering region in the gated part of the sample, in between of its undisturbed parts (ideal leads). The dependence of the resistance on the gate voltage and the number of available channels within the ideal leads are discussed.The author wishes to thank to Professor P. Steda for cooperation and to Professor L. Smrka for his encouragement and support. Dr. R. J. Haug should be acknowledged for providing his experimental results.     

Theory of electronic transport in two-dimensional systems in the presence of magnetic fields

The paper of three parts is focused on the Landauer-Büttiker approach to the study of transport in two-dimensional electron systems, with particular attention to the influence of an external magnetic field. In the previous part the total conductance of such a system was shown to be proportional to the transmission current. In the present part we give a detailed proof, based on the linear response theory, to the last statement. The value of the magnetic field may be arbitrary and possible inhomogeneity of the electric field is also considered.The author wishes to thank to Professor P. Steda and Professor L. Smrka for discussions and encouragement.     

Self-diffusion of V-48 in the FeV σ-phase and in an Fe-47 wt.% V solid solution

Self-diffusion coefficients of vanadium in the FeV -phase and in the corresponding -solid solution (Fe-47 wt.% V) measured in the temperature ranges 1002–1115 °C (-phase) and 1230–1320 °C are reported. The found results differ fundamentally and significantly from the relations in ordered and disordered solid solutions [9]. The diffusivity in -phase at the transition temperature (T _/=1200 °C) is cca 14 times lower than the diffusivity in the b.c.c. solid solution, the chemical composition of which is the same. The lowering is caused by the different values of frequency factors,D _O=0.11 cm²/s andD _O=45 cm²/s. The effect of the corresponding activation enthalpiesH =252 kJ/mole andH =293 kJ/mole is small and quite opposite. The occurence of higher activation enthalpyH in the -solid solution at temperaturesT>T _/ may be attributed to a certain amount of the f.c.c. phase coexisting in the b.c.c. matrix at concentrationsc _v>27 wt.% at sufficiently high temperatures [7]. A comparison of vanadium self-diffusion characteristics measured in the -phase to the extrapolated values obtained on the basis of the previous measurements [1] in the Fe-V primary solid solutions ₁ shows that the diffusivity ratioD ₁/D (1473 K)=33 and that the activation enthalpyH is by about 3% higher than the valuesH ₁ (eq. (5)) measured in the uniphase b.c.c. solid solutions.     

Mechanism and nanosize products of the sol-gel reaction using diphenylsilanediol and 3-methacryloxypropyltrimethoxysilane as precursors

We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm.     

RP-HPLC study of redox equilibria in vanadium-PAR binary and ternary systems: Direct determination of vanadium in steel

The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C₁₈ column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H₂O₂-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH₂OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH₂OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel.     

A novel agarofuran sesquiterpene, celahin D from Celastrus hindsii Benth

A novel agarofuran sesquiterpene polyol ester, 1beta,2beta,6alpha,15beta-tetracetoxy-8 beta,9alpha-dibenzoyloxy-beta- dihydroagarofuran (celahin D) (1), two known analogues of 1,1beta-acetoxy-8beta,9alpha-dibenzoyloxy-4al pha6alpha-dihydroxy-2beta(alphamethylbutanoyloxy)-beta-++ +dihydroagarofuran (2) and beta-acetoxy-8beta,9alpha-dibenzoyloxy-6alpha-hy droxy-2beta(alpha -methylbutanoyloxy)-beta-dihydroagarofuran (3), and a known cytotoxic sesquiterpene pyridine alkaloid, emarginatine E (4) were isolated from the stems of Celastrus hindsii Benth. Three known triterpenes, loranthol (5), lupenone (6) and friedelinol (7) were also obtained from the titled plant. Structural elucidation of compound 1 was established by 2D NMR spectra.     

Photochemical syn-anti isomerization reactions in N2-hydroxyisocytosines--an experimental matrix isolation and theoretical study

N2-hydroxyisocytosine and 1-methyl-N2-hydroxyisocytosine were studied using a matrix isolation technique combined with infrared absorption spectroscopy. For N2-hydroxyisocytosine isolated in an Ar matrix (at 10 K), two imino-oxo isomers, one with the hydroxyimino =N-OH group directed toward the N1-H group (the form called further anti) and the second with the =N-OH group directed toward N3-H (syn), were observed in the ratio 1.4:1. The syn isomer is converted totally to the anti form after UV (lambda > 295 nm) irradiation of the matrix. A small amount of the N(3)H-hydroxy-amino tautomer of N2-hydroxyisocytosine was also detected in the matrix. This form did not react photochemically. For 1-methyl-N2-hydroxyisocytosine, only the syn form of the imino-oxo tautomer was observed after deposition of the matrix. UV (lambda > 295 nm) irradiation induced a photoreaction converting this isomer into the anti form. After 15% of the starting material had been converted into the product, a photostationary state was achieved, and no further progress of the reaction was observed. Subsequent UV irradiation (lambda > 335 nm) caused a back reaction, leading to a disappearance of the anti form and to the recovery of the initial syn isomer. All isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-31G(d,p) level, where DFT is the density functional theory. Good agreement between the observed and predicted patterns of the spectral lines allowed for reliable identification. The experimental IR spectra were interpreted and discussed. The relative energies of the 12 isomers of N2-hydroxyisocytosine were calculated at the MP2/6-31G(d,p) and MP4//MP2/6-31G(d,p) levels. For six isomers of 1-methyl-N2-hydroxyisocytosine, the calculations were carried out at the MP2/6-31G(d,p) level. The anti form of the imino-oxo tautomer of N-hydroxyisocytosine and the syn form of the imino-oxo tautomer of 1-methyl-N2-hydroxyisocytosine were predicted to be the most stable.     

Structural studies of 4-aryloctahydro-pyrido[1,2-c]pyrimidine derivatives

¹³C cross-polarisation magic angle spinning NMR data have been reported for four derivatives of 4-aryl-octahydro-pyrido[1,2-c]pyrimidine-1,3-dione and the X-ray diffraction data for two (with 2′-Me and 2′-OMe). The crystal structures show the presence of centrosymmetric cyclic dimers with intermolecular C1O?H-N or C3O?H-N hydrogen bonds, the configuration at the chiral centres (C4 and C4_a) was determined as RR (SS). The twisting of aromatic ring at C4 with respect to the pyrido[1,2-c]pyrimidine skeleton is about 68-109°.     

Anhydrous Deprotection of Dimethyl Acetals with Acetyl Chloride/ZnCl2

Dimethyl acetals are converted to the corresponding aldehyde in THF with acetyl chloride/zinc chloride in the presence of dimethyl sulfide