Synthetische Juvenilhormone 3. Mitteilung. p-Substituierte 4-Phenyl-buten(1)-carbonsäurederivate

The syntheses of p-substituted 2-methyl-4-phenylbuten(1)-carboxylic acid derivatives are described, using Blanc's chloromethylation reaction, the Friedel-Crafts alkylation of unsaturated ketones or the Meerwein arylation; the formed intermediates react in subsequent steps to the title compounds.     

Monocyclopentadienylhydride derivatives of ruthenium: stereoselective proton transfer and proton-hydride exchange in an extremely short dihydrogen bond

Diastereomerically pure complexes of formula CpRuCl(PP) and CpRuH(PP) with chiral ferrocenyl diphosphines were prepared and the selectivity of proton-transfer processes over the monohydride compounds with different acids was studied. With 1 equiv of HBF(4) the cis-dihydrogen and trans-dihydride complexes were formed while with 3 equiv of CF(3)CO(2)H the trans-dihydride derivative was the only product. However, the use of 1 equiv of CF(3)CO(2)H led to a dihydrogen bonded complex with an extremely short RuH...HO(2)CF(3) interaction that exhibits proton-hydride exchange. Using the labeled acid CF(3)CO(2)D, a stereoselective transference of the deuteron was demonstrated that implies the previous epimerization of the monohydride and the subsequent attack of the acid in the position previously occupied by the hydride.     

Ab initio study of AmCl(+): f-f spectroscopy and chemical binding

A valence full configuration interaction study with a polarized double-zeta quality basis set has been carried out for the lowest 49 electronic states of AmCl(+). The calculations use a pseudopotential treatment for the core electrons and incorporate a one-electron spin-orbit interaction operator. Electrons in the valence s, p, d, and f subshells were included in the active space. The resulting electronic potential energy curves are largely repulsive. The chemical bonding is ionic in character with negligible participation of 5f electrons. The molecular f-f spectroscopy of AmCl(+) arises essentially from an in situ Am(2+) core with states slightly redshifted by the presence of chloride ion. Am(+)+Cl asymptotes which give rise to the few attractive potential energy curves can be predicted by analysis of the f-f spectroscopy of isolated Am(+) and Am(2+). The attractive curves have substantial binding energies, on the order of 75-80 kcal/mol, and are noticeably lower than recent indirect measurements on the isovalent EuCl(+). An independent empirical correlation supports the predicted reduction in AmCl(+) binding energy. The energies of the repulsive curves are strongly dependent on the selection of the underlying atomic orbitals while the energies of the attractive curves do not display this sensitivity. The calculations were carried out using our recently developed parallel spin-orbit configuration interaction software.     

Carbometallate: Komplexe Anionenverbände [MoC4/26—] in der Kristallstruktur von Pr[MoIIC2]

Carbometalates: Complex Anions equation/tex2gif-stack-4.gif [MoC_4/2^6—] in the Crystal Structure of Pr equation/tex2gif-stack-5.gif [Mo^IIC₂] Criteria for the existence of carbometalates are established and discussed in a broader context. The concept is then applied to the novel compound Pr₂[MoC₂], which is characterized by chemical analyses, X‐ray diffraction and metallography. The crystal structure (tetragonal, P4₂/mnm, Z = 4, a = 581.29(8) pm, c = 1032.53(14) pm) consists of layered polyanions equation/tex2gif-stack-6.gif[MoC_4/2^6—] of distorted vertex and edge sharing MoC₄ tetrahedra. Praseodymium is also in a distorted tetrahedral coordination by carbon. The physical properties show “bad metal” behaviour and localized magnetic 4f‐moments in agreement with the existence of Pr³⁺‐species. A detailed bonding analysis using both the electron localization function ELF and the COHP method justifies the interpretation of the title compound as a carbomolybdate(II).     

A New Generation of "Cholaphanes": Steroid-Derived Macrocyclic Hosts with Enhanced Solubility and Controlled Flexibility

The macrocyclic "cholaphanes" 3a-c were synthesized from the inexpensive steroid cholic acid. Like earlier relatives they feature substantial cavities with inward-directed hydroxyl groups, suitable for binding polar molecules such as carbohydrates in nonpolar media. New features are the externally directed alkyl chains, promoting solubility in organic solvents, and (in the case of 3b/c) reduced conformational freedom resulting from truncation of the steroidal side-chain. In particular, modeling shows that the smallest macrocycle 3c possesses very little flexibility, preferring an open conformation which is also revealed in the X-ray crystal structure of its pentahydrate. NMR studies indicated that all three cholaphanes form 1:1 complexes with octyl beta-D-glucoside in CDCl(3), with K(a) = 600-1560 M(-)(1). Cholaphanes 3b/c proved able to extract methyl beta-D-glucoside from aqueous solutions into CHCl(3). The transport of methyl beta-D-glucoside across a chloroform barrier was also demonstrated for 3c.     

Pfropfcopolymerisation von Cellulose mit zwei Vinylmonomeren

Zusammenfassung Die vorliegende Arbeit stellt eine Beschreibung von Experimenten dar, die die Erhöhung der Pfropfbereitschaft von trägen Komponenten durch Beimischung von aktiveren zum Ziele hatten.Das Trägermolekül war in allen Fällen Cellulose in Form von hochgradig gereinigtem Zellstoff. Durch die Verwendung von Mischsystemen aus Styrol und Methylmethacrylat gelang es, das trägere Styrol in bedeutend größerer Menge auf die Cellulose aufzupfropfen, als es bei Abwesenheit des aktiven Methylmethacrylats der Fall war.

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Grafting Polymerization of Cellulose with Two Vinyl Monomers

This paper describes experiments to increase the grafting of cellulose with components of poor reactivity by mixing them with highly reactive ones. A highly purified wood pulp was used as backbone. Using combinations of styrene and methyl methacrylate it was possible to graft considerably higher amounts of the poorly reacting styrene than in the absence of the highly reactive methyl methacrylate.

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Nach einem Vortrag, den der erstgenannte der Autoren im Rahmen der Arbeitstagung des Vereins Österreichischer Chemiker am 27. September 1968 in Wien gehalten hat.     

Thin-layer chromatography combined with diode laser desorption/atmospheric pressure chemical ionization mass spectrometry

The desorption of an analyte by a continuous wave diode laser from a porous surface of a thin-layer plate covered with a graphite suspension is presented. The thermally desorbed analyte molecules are ionized in the gas phase by a corona discharge at atmospheric pressure. Therefore, both essential processes--the desorption and the ionization of analyte molecules, which are often performed in one step--are separated. The target preparation is easy and fast since no additional extraction process is required. The mass spectrometric background signal was mostly limited to the low mass range showing no interference with typical compounds of interest. In this study, the calmative and antihypertensive drug reserpine was chosen as model analyte, which is often used for specification of mass spectrometers. No fragmentation was observed because of efficient collisional cooling under atmospheric pressure. The influence of diode laser power and the composition of the graphite suspension were investigated, and a primary optimization was performed.     

Conformation and internal mobility of 5H-dibenzo[a,d]cycloheptene derivatives in solution. Conformational analysis of highly flexible structures,part II

Summary The conformational possibilities of 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cycloheptene (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2), and 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (3) are analysed using empirical force field methods. Minimum energy conformations, interconversion pathways, interconversion graphs and interconversion energies are examined in view of the analysis of conformer equilibria of1,2, or3 in solution. In addition, some basic requirements of the analysis of fast interconverting conformers using the lanthanide induced shift method are discussed.

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Konformation und interne Beweglichkeit von 5H-Dibenzo[a,d]cyclohepten Derivaten in Lösung. Konformationsanalyse hochflexibler Strukturen, Teil 2

Zusammenfassung Die konformativen Möglichkeiten von 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cyclohepten (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (2) und 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (3) wurden mit Hilfe empirischer Kraftfeldmethoden analysiert. Jene Konformationen, die einem energetischen Minimum entsprechen, sowie Interkonversionswege, Interkonversionsgraphen und Interkonversionsenergien wurden in Hinblick auf die Analyse der Konformerengleichgewichte von1,2 oder3 in Lösung untersucht. Weiters werden noch einige grundlegende Voraussetzungen für die Analyse von sich schnell ineinander umwandelnden Konformeren mittels der Lanthaniden-induzierten Verschiebungsmethode besprochen.

     

Chemistry of polyfunctional molecules-123. Reactions of BiBr3, SbI3 and AsI3 with LiN(PPh2)2; X-ray structure of a cyclophosphazene salt containing arsenic(I)

BiBr₃ or SbI₃ react at 20°C with LiN(PPh₂)₂ (1) to give elementary Bi or Sb and the P---P coupled phosphazene ligand Ph₂P---N=PPh₂---PPh₂=N---PPh₂ (2). The reaction of AsI₃ with 1 at room temperature formed yellow needles of the eight-membered heterocycle (3), whereas AsI₃ interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI₃ and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium(I) salt

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I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis.