Synthesis of a cyclic dinuclear organotin carboxylate via simultaneous debenzylation and decarbonylation reactions: X-ray crystal structure of [(PhCH2)2{O2CC6H4{N(H)N(C6H3-4(O)-5-O)}-o}Sn]2

The complex, [(PhCH₂)₂{O₂CC₆H₄{N(H)N(C₆H₃-4(O)-5-O)}-o}Sn]₂ (1), is obtained as the exclusive reaction product from the reaction of sodium 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl]benzoate and (PhCH₂)₃SnCl. The reaction possibly proceeds via Dakin type rearrangements where arylazosalicylaldehyde is oxidized to arylazocatechol, followed by facile Sn-C bond cleavage. Complete assignments were achieved by ¹H, ¹³C, 2D ¹H-¹¹⁹Sn HMQC (¹¹⁹Sn chemical shift), 1D gs ¹H-¹⁵N HMQC (¹J(¹⁵N, ¹H) coupling constant) NMR and ESI-MS. The crystal structure of compound 1 as determined by X-ray diffraction analyses shows a cyclic centrosymmetric dinuclear moiety linked into extended chains by pairs of long Sn?O contacts of approximately 3.2 Å. Two polymorphs were identified and their structures differ primarily in the packing arrangement afforded by the benzyl groups. In one polymorph, when viewed along the Sn?Sn vector, the benzyl groups at each Sn-atom are oriented to form an S-shape, while they form a U-shape in the second polymorph.     

Study of the carbonyl products of terpene/OH radical reactions: detection of the 2,4-DNPH derivatives by HPLC-MS

The oxidation of the terpenes - and -pinene, limonene and ³-carene by hydroxyl radicals has been investigated in a fast-flow reactor coupled to a liquid nitrogen trap for collecting the carbonyl compounds. Identification of the products was performed via 2,4-dinitrophenylhydrazone (DNPH) derivatization of the carbonyls to form the mono- and di-DNPH derivatives, which were analysed by high-performance liquid chromatographic (HPLC)-DAD (diode array detector) and HPLC-mass spectrometry (HPLC-MS). Both electrospray ionization [ESI(–)] and atmospheric pressure chemical ionization [APCI(–)] were suitable for the detection of the DNPH derivatives of formaldehyde, acetaldehyde, myrtanal, campholene aldehyde, perillaldehyde, acetone, nopinone, trans-4-hydroxynopinone and 4-acetyl-1-methylcyclohexene. Also the mono-DNPH derivatives of the dicarbonyl compounds pinonaldehyde, endolim and caronaldehyde could be identified. The MS² spectra generated in the ion trap of the mass spectrometer allowed us to distinguish between aldehydes and ketones on the basis of the characteristic fragment ion m/z 163 for the aldehydes. For the quantitative analysis of the mono-DNPH derivatives, ESI(–) in combination with single ion monitoring (SIM) detection showed the lowest detection limits. For the quantification of the dicarbonyl compounds, the acid-sensitive di-DNPH derivatives had to be formed by keeping the acidity in the acid-catalysed derivatization reaction at about 1.7 mM H₂SO₄. Detection of these dicarbonyl compounds can only be performed by APCI(–) with somewhat lesser sensitivity than by HPLC-DAD.     

<Emphasis Type="Italic">o</Emphasis>-Phenylenediamine as a New Catalyst in the Highly Regioselective Conversion of Epoxides to Halohydrins with Elemental Halogens

Summary. The regioselective ring opening of epoxides using elemental iodine and bromine in the presence of o-phenylenediamine as a new catalyst affords vicinal iodo alcohols and bromo alcohols in high yields. The major advantages of this method are versatility, high regioselectivity, a cheap and commercially available catalyst, mild and neutral reaction conditions, and short reaction times. Fourier transform Raman spectroscopy was used to study the reaction of iodine with o-phenylenediamine. The results indicate that the complex [(Diamine)I]⁺·I₅^– is formed, and we suggest that the major nucleophile is the pentaiodide ion. This bulky nucleophile has a fundamental role in the high regioselectivity observed attacking the less sterically hindered epoxide carbon.     

Hydrogen bonding interactions between indole and benzenoid-pi-bases

The NH-pi interactions of indole with benzene, naphthalene, phenanthrene, toluene, m-xylene, and mesitilene, in carbon tetrachloride solutions, have been studied by Fourier transform infrared spectroscopy. The experiments, carried out on the NH stretching band of indole, prove the formation of 1:1 complexes in which the NH bond of indole is engaged. The NH frequency shifts are independent of the number of rings in the base, but they progressively increase as the electron density is enhanced by methylation. The association constants increase with the increase of both, the number of rings and the methyl groups on the base. At higher base concentrations, further shifts on the free NH and associated bands indicate the formation of 1:2 complexes, which suggest hybride NH-pi and van der Waals interactions between one indole ring and two benzene acceptor molecules.     

Separation of the enantiomers of phenprocoumon and warfarin by high-performance liquid chromatography using a chiral stationary phase. Determination of the enantiomeric ratio of phenprocoumon in human plasma and urine

The enantiomers of the chiral coumarin-type anticoagulants phenprocoumon, warfarin and p-chlorophenprocoumon were separated by high-performance liquid chromatography on a chiral stationary phase (Nucleosil-Chiral 2) and normal-phase conditions. Chromatographic peak identification was performed with authentic reference compounds of the enantiomers and on-line UV spectra comparison. This method was applied to the determination of the enantiomeric ratio of phenprocoumon in plasma and urine extracts from patients under racemic drug therapy. The limit of detection (50 and 80 ng/ml) and precision (less than 5%) of the method are adequate for pharmacokinetic and enantioselective disposition studies, respectively, of phenprocoumon. No racemization was detected during the extraction procedures.     

Diffraction dissociation of nuclei in 450 GeV/c proton-nucleus collisions

Diffractive dissociation of nuclei (Be, Al, W) in collisions with 450 GeV/c protons,pApX, has been measured with the HELIOS spectrometer at the CERN Super Proton synchrotron. The dependence of the single-diffraction cross-section on the nuclear massA can be parametrized as _SD mb×A ^0.35±0.02, showing the peripheral nature of the process. The differential cross-section d_SD=(3.8±0.3)mb ×A ^0.35±0.02, is exponential with the slope parameter, increasing from 6.2±0.4 (GeV/c)^–2 for beryllium to 7.9±0.5 (GeV/c)^–2 for tungsten. The slope parameter also increases with increasing massM _X of the diffractively produced state. The rapidity, multiplicity, and transverse-momentum distributions of the particles of the diffractively produced stateX show a longitudinal phase-space population and are remarkably insensitive to the nuclear mass. This, together with theA ^1/3 dependence of _SD, suggests that the dominant process of nuclear diffractive excitation is the dissociation of single nucleons.Deceased     

Inductively-coupled plasma atomic emission spectroscopic determination of trace impurities in ZrO2-powder

Four independent procedures including one using slurry nebulization ICP-AES were developed for the trace analysis of ZrO₂ powders. They were evaluated with respect to detection limits, blank values, interferences, accuracy and precision. For the procedures I–III ZrO₂ powder was decomposed by fusion with a 10-fold excess of NH₄HSO₄ and subsequent dissolution of the melt in either water or, after evaporation of NH₄HSO₄, in diluted HNO₃. In procedure I the solution was directly analyzed by ICP-AES, which was optimized with the aid of a simplex algorithm. In procedure II Zr was separated by extraction from 6 mol/l HNO₃ with a 0.5 mol/l solution of 2-thenoyltrifluoroacetone (TTA) in xylene. More than 99.5% of the Zr was removed and more than 95% of the trace elements retained. In procedure III the matrix was separated by its precipitation as ZrOCl₂·8 H₂O from a (1:4) HCl-acetone medium. More than 98% of Zr were removed and more than 90% of the trace elements were retained. In procedure IV the ZrO₂ powder was dispersed by ultrasonic treatment in water acidified with HCl (pH 2) and the slurry was directly analyzed by ICP-AES using a Babington nebulizer. The optimization and the analytical features of this procedure will be described in a subsequent paper. In all procedures the calibration was performed by standard addition and matrix matching was not necessary. The detection limits varied from 0.3 g/g (Ca) to 10 g/g (Al). The standard deviations obtained were 1–10% depending on the element and its concentration in the sample. The results of the procedures for 6 commercially available fine ZrO₂ powders were found to agree for Al, Ca, Fe, Mg, Na, Ti and Y. A good agreement between the results of the procedures using matrix separation was also observed for Cu, Mn, V, but the concentrations of these elements found by methods without matrix separation were considerably higher. Except for Ca and Mg the blank values encountered were below the detection limits.On leave from Department of Analytical Chemistry, Technical University, PL-00-664 Warsaw, Poland