A vibrational molecular force field of model compounds with biological interest. I. Harmonic dynamics of crystalline urea at 123 K

Normal coordinate calculations have been performed for urea and deuterated urea in the crystalline state. We have used the modified Urey–Bradley–Shimanouchi intramolecular potential energy function and a rather sophisticated intermolecular energy function to reproduce I.R. and Raman frequencies with an average error of 2 cm^–1. The general agreement between the calculation and experiment suggests that intermolecular interactions must be taken into account to determine reliable intramolecular parameters of the potential energy function, mainly the barrier to internal rotation around the C? N bond. The intermolecular energy function, which consists of the Buckingham function and an explicit harmonic function for hydrogen-bonding, then has the merit to reproduce quite well the observed frequencies of lattice vibrations.     

Bestimmung der Oberfl?chenzusammensetzung von Calcit in Mg2+-haltigen Ca-45-markierten L?sungen

Zusammenfassung Über den Ca²⁺-Mg²⁺-Ionenaustausch wurde der Mg²⁺-Ionengehalt in Calcitoberflächen in Abhängigkeit von der Mg²⁺-Konzentration in Ca-45-markierten Lösungen bestimmt. Es wurde gefunden, daß der Anstieg des Molverhältnisses Mg/Ca in der Calcit-Oberfläche bei steigendem Mg²⁺-Gehalt in der Lösung jeweils bei Erreichen von Mg/Ca 1 und 3 deutlich verringert wird. Die ermittelte Austauschisotherme kann benutzt werden, um über eine Bestimmung des Mg/Ca-Verhältnisses in der Lösung auf dasjenige in der Oberfläche zu schließen.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen.     

Optically detected magnetic resonance study of the lowest excited triplet state of aromatic thioketones: Xanthione

The aromatic thioketone xanthione has been investigated by means of the optically detected magnetic resonance (ODMR) technique in a n-hexane matrix at ≈ 1.1 K. It was established that the short-lived red emission, which is characteristic for many thione molecules, is phosphorescence. At high temperatures (77 K) this phosphorescence originates mainly (>80%) from the T₁^z (n, π*) sublevel (k_z^(r) >k_x^(r), k_y^(r). At low temperature (1.1 K) the intersystem crossing following S₂ (π, π*) ← S₀ excitation is a highly spin-sublevel selective process which populates predominantly the T₁^x and T₁^y, levels. Hence, the slow spin—lattice relaxation phosphorescence at low temperature originates from these sublevels. A value of 0.0611 cm^?1 was obtained for the zero-field parameter |E|/hc. A lower limit of 0.66 cm^?1 has been found for the zero-field parameter |D|/hc. This value is considerably larger than those observed for ketones, and it is shown that spin—orbit coupling contributes strongly to the zero-field splitting.     

Grignard-Addition an Pyridin-N-oxid

Addition of phenyl-, alkyl-, alkenyl- and alkinyl-Grignard reagents to pyridine-N-oxide in THF leads to 5-substituted (2Z, 4E)-pentadien-aldoximes 6 having (E) (syn)-configuration of the C, N-double bond. The unsaturated oximes are shown to arise through an electrocyclic ring opening reaction from the primary Grignard adducts 5 . These can be trapped by protonation at low temperature.     

Horminon,Taxochinon und weitere Royleanone aus 2 abessinischen Plectranthus-Spezies (Labiatae)

Horminone, taxoquinone and other royleanones, obtained from two Abyssinian Plectranthus species (Labiatae). From the coloured glands on the leaves of two botanically unclassified Plectranthus sp. from Abyssinia, a series of royleanones has been isolated, namely royleanone ( 1 ) and 6,7-dehydroroyleanone ( 2 ) from one species, and 6,7-dehydroroyleanone, horminone ( 3 ), taxoquinone ( 4 ), 6β, 7α-dihydroxyroyleanone ( 5 ), 7α-acetoxy-6β-hydroxyroyleanone ( 6 ) and 7-oxoroyleanone ( 7 ) respectively, from the other.     

The Crystal and Molecular Structures of Two Acid-Catalysed Rearrangement Products of Taxochinon

The structures of two acid catalysed rearrangement products of taxochinone ( 1 ) have been determined by X-ray analysis. One of the products turned out to be a 20 (10→9) abeo-abietane ( 2 ), the other an optically inactive phenalenone ( 3 ). Crystals of the former compound, C₂₀H₂₆O₃, belong to space group P2₁2₁2₁ with four molecules per cell and the structure was refined with 879 significant reflexions to R = 0.032. Crystals of the latter compound, C₂₀H₂₂O₂, belong to space group P2₁/c with 12 molecules per cell and the structure was refined with 1823 significant reflexions to R = 0.058.     

The Bond-Rotational Mobility of Guanidinium Ion

The NMR. spectrum of guanidinium ion 1 is studied in anisotropic liquid crystalline nematic solution. Assuming an HNH-angle of 120°, the distance ratio NH /NC = 0.784 is obtained, from which using NC = 1.330 Å (from X-ray data) NH = 1.043 Å results. An upper bound for the free energy of activation for bond rotation of ΔG⁺ ≤ 13 kcal/mol is deduced. The bondrotational mobility of 1 is also investigated using the MINDO/3-SCF-procedure. The results obtained for the three conceivable consecutive activation energies for bond-rotation indicate that the observed bond-rotational mobility of 1 does not involve cooperative two- or three-bond rotations. The ‘conjugative stabilization’ of 1 has been estimated to be of the order of 24–26 kcal/mol.     

Chelatometrie. X

Zusammenfassung Eriochromrot B ist ein gut geeigneter komplexometrischer p_M-Indicator, der in manchen Beziehungen Vorteile gegenüber anderen Indicatoren aufweist. Mit seiner Hilfe lassen sich z. B. bei p_H 6,5 Zink-Ionen und bei p_H 10 Zink- und Blei(II)-Ionen mit 0,1 m Äthylendiamintetraessigsäure (EDTA)-Lösung bestimmen. Bei der Zinkbestimmung im schwach sauren Milieu können kleinere Kupfer(II)-, Palladium(II)- sowie Platin(IV)-Ionenkonzentrationen mit Thioharnstoff (TH) maskiert werden. In ammoniakalischer Lösung ist die Zinktitration neben Bariumsulfat möglich. Dadurch läßt sich der Zinkgehalt in Lithopone ermitteln.Das Verhalten von Kupfer(II)-Ionen zu Eriochromrot B und EDTA wird beschrieben.Die komplexometrischen Eigenschaften des Cadmiums sind denen des Zinks analog. Über eine Manganbestimmung wird später berichtet.Untersuchungen über p_M-Indicatoren werden an weiteren Pyrazolonfarbstoffen fortgesetzt.Mitteilung IX dieser Reihe: diese Z. 153, 249 (1956).Der I. R. Geigy A.-G., Basel, danke ich für die freundliche Überlassung einiger Reagentien, insbesondere für Eriochromrot B. Herrn W. Johannsen, dem Laboratoriumsleiter der Metallhütte Mark A.G., bin ich für sein Interesse an dieser Arbeit verpflichtet.     

Chloracylierung und Bromacylierung von Carbonylverbindungen: Eine in Vergessenheit geratene Carbonylreaktion. I. Präparative Anwendungsbreite

Chloroacylation and bromoacylation of carbonyl compounds: A forgotten carbonyl reaction. I. Scope of the reaction Aliphatic, α,β-unsaturated and aromatic aldehydes as well as aliphatic ketones react with acyl halides to (α-haloalkyl)esters. These bifunctional derivates contain two leaving groups of different reactivity. The scope of this scarcely of this scarcely known carbonyl reaction is discussed.     

Regiochemistry of nucleophilic displacements in chloroquinones

Nucleophilic displacement of halide from 2-halo 1,4-quinones occurs at the $\text{ipso}$ carbon or at the carbon vicinal to it depending on the nature of the nucleophile and the solvent.