Radical mediated synthesis of 6-arylphenanthridines via benzotriazole ring-opening

Lithiation of diarylbenzotriazol-1-ylmethanes followed by addition of copper( I ) iodide gave 6-arylphenanthridine derivatives in moderate yields. When the two aryl groups were the same or contained very different electron densities, only one product was obtained. However, when the two aryl groups exhibited electron densities of similar magnitude, two isomers were afforded. According to the substituent effect, we believe that the reactions proceed via radical intermediates formed by copper( I ) iodide.     

Struktur von 7,11-Diphenyl-2,4-diazaspiro[5,5]undecan-1,3,5,9-tetraonen durch LIS-NMR

A semi-quantitative method for determining distances between a possible coordination centre and protons from LIS-NMR values is developed for the title compounds3, although these have four coordination points. This makes it possible to propose structures and conformations for the isomers of3.

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Mit 4 Abbildungen

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H.-H. Otto undH. Yamamura, Ann. Chem., im Druck.     

Dynamics of photodissociation of 3,3,3-d(3)-propene at 157 nm: site effect and hydrogen migration

In a preceding paper [Lee et al., J. Chem. Phys. 119, 827 (2003)], we measured the kinetic-energy distributions P(E(t)) and branching ratios of products from photolysis of propene at 157 nm using time-of-flight spectroscopy combined with photoionization. In the present work, hydrogen migration before fragmentation and a site effect on P(E(t)) and branching ratios were revealed from the photodissociation of CD(3)CHCH(2). Labeling of the methyl group with deuterium enabled us to differentiate between elimination of atomic and molecular hydrogen from the vinyl moiety and from the methyl moiety; the P(E(t)) and relative yields for the formation of H, D, H(2), HD, and D(2) were measured. Deuterium labeling allowed us to also differentiate the fragmentation after hydrogen transfer from that before hydrogen migration. The observation of isotopic variants of CD(3) and C(2)H(3) radicals in the C-C bond cleavage provides evidence for hydrogen transfer of propene because of site specificity. The fraction of fragmentation after hydrogen transfer is estimated to be 25%. The isotope-specific branching ratios for five dissociation pathways of CD(3)CHCH(2) were evaluated.     

Regiospecifically controlled formation of tetrasubstituted tributyltin ketone enolates catalyzed by a palladium complex

The palladium-catalyzed hydrostannolysis of α-disubstituted allyl β-keto esters yields the corresponding tributyltin β-keto carboxylates which loose carbon dioxide at very moderate temperature, thus leading to the regiospecific formation of tributyltin tetrasubstituted enolates.     

Asymmetric synthesis of cis-5-tert-butylproline with metal carbenoid NH insertion

The highly stereoselective intramolecular metal carbenoid insertion reaction of sulfinimine-derived delta-amino alpha-diazoesters is used to prepare cis-5-tert-butylproline. A concerted or nearly concerted metal carbenoid N-H insertion reaction mechanism is proposed.     

Determination of the pesticides Chlorpropham,Propham, Propoxur,and Terbucarb by low temperature phosphorimetry

Summary Simple, direct, and sensitive low temperature phosphorimetric methods for the determination of Chlorpropham, Propham, Propoxur, and Terbucarb in EPA solvent are described. The minimum detectable amounts are 0.01 p. p. m. for Chlorpropham and Propham and 0.02 and 0.3 p. p. m. for Propoxur and Terbucarb respectively. The ranges of linearity of the analytical calibration graphs are 0.05-7.5, 0.05–10, 0.5–50, and 1–50 p. p. m. for Chlorpropham, Propham, Propoxur, and Terbucarb respectively. The procedure for Chlorpropham has been applied to the analysis of a solid commercial formulation.

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Bestimmung der Pesticide Chlorpropham, Propham, Propoxur und Terbucarb bei Tief-Temperatur-Phosphorimetrie

Zusammenfassung Einfache, direkte und empfindliche Methoden für die Bestimmung der genannten Pesticide in dem Lösungsmittel Diethylether-i-Pentan-abs. Ethanol wurden beschrieben. Die geringsten nachweisbaren Mengen sind 0,01 ppm für Chlorpropham und Propham sowie 0,02 und 0,3 ppm für Propoxur und Terbucarb. Die Eichkurven verlaufen zwischen 0,05 und 7,5, 0,05 und 10, 0,5 und 50 sowie zwischen 1 und 50 ppm für Chlorpropham, Propham, Propoxur bzw. Terbucarb linear. Das Verfahren für Chlorpropham wurde zur Analyse eines festen Handelsproduktes angewendet.

     

Studium des gegenseitigen Einflusses der Bindungen in Thiocyanat-Kupfer(II)-Komplexen mit Methyl- und Dimethylpyridinen mittels Infrarotspektroskopie

The infrared spectra of thiocyanato-copper(II) complexes of the type Cu(NCS)₂ L ₂ with all isomeric picolines and lutidines (L) as well as those of the type Cu(NCS)₂ L ₃ withL=3- and 4-picoline, 3,4- and 3,5-lutidine were measured. The behaviour of the (CN) stretching vibrations of the Cu(NCS)₂ L ₂ complexes led to conclusions on the different kind of coordination of the NCS groups in dependence on the ligandL. The mutually conditioned strength of the Cu–NCS and Cu–N(L) bonds in the equatorial plane, especially in the presence of ligandsL with the steric effect, was determined from the frequency shift of the Cu–NCS and Cu–N(L) stretching vibrations with regard to the vibrations for Cu(NCS)₂(pyridine)₂.

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Optimal double-configuration study of the lowest excited Π states of H2

Various levels of approximation (Hartree-Fock, configuration interaction and double-configuration Hartree-Fock method) are compared for extensive and limited exponent optimization of the atomic orbitals of the wavefunctions. The potential energy curves for the lowest-lying ¹ _u, ³ _u, ¹ _g, ³ _g states of the hydrogen molecule are presented. The shapes of the curves on the highest level of approximation, i.e. with the optimal double-configuration wavefunction, are basically in agreement with previous, more sophisticated and time-consuming work. The influence of the various approximations is also studied for several one-electron properties: charge distribution of the wavefunction along and perpendicular to the molecular axis, quadrupole moment and core attraction energy distribution. Differences arise to the work of Zemke et al. [1], who used a limited exponent optimization with a larger basis set, in the _g states where the orbitals are very diffuse. The differences concern magnitude and location of minima and maxima of potential curves, as well as considerable changes in one-electron properties which depend strongly on the spatial distribution of the orbitals.

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Zusammenfassung Verschiedene Approximationsstufen (Hartree-Fock, Konfigurationenwechselwirkung und Doppelkonfigurationen-Hartree-Fock-Methode) werden für ausgedehnte und begrenzte Exponentenoptimisierung von Atomorbitalen der Wellenfunktionen verglichen. Die Potentialkurven für die niedrigsten ¹ _u, ³ _u, ¹ _g, ³ _g Zustände des Wasserstoffmoleküls werden angegeben. Die Form der Kurven im Rahmen der besten Näherung, d. h. mit Doppelkonfiguration, stimmen im wesentlichen mit früheren aufwendigeren Rechnungen überein. Der Einfluß der verschiedenen Approximationen wird auch an einigen Einelektroneneigenschaften studiert: Ladungsverteilung der Wellenfunktion längs und senkrecht zur Molekülachse, Quadrupolmoment und Verteilung der Rumpfenergie. Unterschiede erscheinen zur Arbeit von Zemke et al. [1], die einen größeren Basissatz mit begrenzter Optimisierung verwandten, bei den _g Zuständen, wo die -Orbitale sehr diffus sind. Die Unterschiede betreffen Größe und Lage der Minima und Maxima der Potentialkurven sowie beträchtliche Änderungen in solchen Einelektroneneigenschaften, die stark von der räumlichen Verteilung der Orbitale abhängen.

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Résumé Comparaison de différents niveaux d'approximation (Hartree-Fock, interaction de configuration et Hartree-Fock à deux configurations) pour des optimisations étendues et limitées des orbitales atomiques de base. Calcul des courbes d'énergie potentielle pour les plus bas états ¹ _u, ³ _u, ¹ _g, ³ _g de la molécule d'hydrogène. Pour la fonction d'onde la plus raffinée: H.F. à deux configurations, la forme des courbes est en accord avec les résultats obtenus dans des travaux précédents plus complexes et plus coûteux. On étudie aussi l'influence des diverses approximations sur plusieurs propriétés monoélectroniques: distribution de charge le long de l'axe moléculaire et perpendiculairement à celui-ci, moment quadrupolaire et distribution de l'énergie d'attraction de coeur. On trouve des différences avec le travail de Zemke et al. (1), qui utilisent une plus grande base partiellement optimisée, pour les états _g où les orbitales sont très diffuses. Les différences concernent la grandeur et la position des extrema des courbes de potentiel, ainsi que des variations importantes des propriétés monoélectroniques qui dépendent fortement de la distribution spatiale des orbitales.

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On leave to: Institut für Theoretische Chemie, Universität Stuttgart.

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On leave to: Office of Computing Activities, National Science Foundation, Washington, D.C.     

Preparation of 1,1,1,3,3-pentafluoropropane (HFC-245fa) by using a SbF5-attached catalyst

In this report, a simple process for preparing HFC-245fa through the reaction of 1,1,1,3,3-pentachloropropane (PCP) and anhydrous HF via two-step vapor-phase catalytic fluorination is described. The antimony pentafluoride catalyst was supported on inert porous materials to improve the catalytic activity. The resulting process catalyst not only exhibited high catalytic activity and excellent thermo-stability, but also improved the performance of SbF₅, in terms of hygroscopicity and corrosion.