The microwave spectrum and dipole moment of 1,1-diflurobenzocyclopropene

The rotational spectrum of 1,1-difluorobenzocyclopropene, measured in the X- and R-bands, has been analysed to give the rotational constants in the ground and first four vibrational states. These constants are in agreement with a structure based on those of crystallographically determined related molecules. Indirect evidence is adduced that the carbon skeleton is indeed planar. The dipole moment in the ground (3.57₂ ± 0.02 D) and first excited state (3.54 ± 0.03 D) has been determined through an analysis of the second-order Stark effect. This high value implies considerable polarisation of the π-electron framework.     

Conformations of fused cycloalkanes in organometallic complexes : IV. The crystal and molecular structure of tricyclo-[6.4.0.02.7]dodeca-3,5-dienetricarbonyliron

The precise molecular structure of the title compound has been determined by single crystal X-ray diffractometry. It consists of a cyclohexadiene ring fused at the 5 and 6 positions to a cyclobutane ring which is in turn fused to a cyclohexane ring. The two six-membered rings are trans to each other with respect to the shared four-membered ring. The Fe(CO)₃ moiety is bound in the usual way to the conjugated diene portion of the cyclohexadiene ring. The feature of greatest interest is the mutual influence of the conformations of the two fused cycloalkane rings, whose intrinsically preferred conformations are mutually incompatible. Under the influence of the fused cyclohexadiene ring the C₄ ring would tend to be planar, while the cyclohexane ring would tend, of itself, to have a chair conformation. The actual result is a compromise, with the C₄ ring being folded by 15° along its diagonal and the C₆ ring having a conformation intermediate between planarity and a chair. Crystallographic data: space group, P2₁, Z = 2. Unit cell dimensions at 3°C are a = 6.176(1), b = 11.307(2), c = 9.781(2) Å and β = 92.89(2)°. A set of 1733 reflections having 2θ(Mo-K_α) < 63.7° and I > σ(I) was refined to convergence (R₁ = 0.055; R₂ = 0.034) with hydrogen atoms refined isotropically and all others anisotropically.     

Determination of boron in nickel-base alloys by the dianthrimide method

The dianthrimide method for the determination of boron in iron and low-alloy steels may be applied to nickel-base materials. The sample is dissolved, without any loss of boron, by hydrochloric and sulphuric acids and the resulting boric acid determined spectrophotometrically with dianthrimide. Background corrections are necessary to compensate for the absorbance from ions such as nickel and iron.     

Die Messung des Kraftverlaufs beim kurzzeitigen Zerreißen von Kunststoffen durch eine Sprengstoffdetonation mittels Dehnungsmeßstreifen

Zusammenfassung Zur Messung der Zugfestigkeit bei kürzesten Beanspruchungszeiten wird eine Prüfapparatur beschrieben, bei der die Beanspruchung des Prüfstabes durch eine Sprengstoffdetonation erfolgt. Durch ein besonders eingebautes Me?element, das aus einem dünnwandigen Stahlrohr mit geeignet angebrachten Dehnungsme?streifen besteht, ist es m?glich, den zeitlichen Verlauf der vor dem Zerrei?en auf den Prüfstab wirkenden Kraft exakt zu messen. Es wird gezeigt, da? durch die besondere Anordnung der Dehnungsme?streifen ein tr?gheitsfreies Messen bis zu einer Zeit von 5 · 10⁻⁵ sec, bei einer Genauigkeit der Kraftmessung von ± 10%, erreicht werden kann. Messungen mit dieser Apparatur an verschiedenen Kunststoffen zeigen, da? das für den kurzzeitigsten Beanspruchungsbereich gewonnene Kurvenstück, das die Abh?ngigkeit der Zugfestigkeit von der Beanspruchungszeit gibt, zwanglos mit der Zugfestigkeit beim normalen Zugversuch mit wesentlich l?ngerer Beanspruchungszeit in Verbindung gesetzt werden kann. Auch Stoffe, die beim üblichen Zugversuch fast gleiche Zugfestigkeiten aufweisen, zeigen im kurzzeitigsten Bereich ein sehr unterschiedliches Verhalten. Ein glas?hnlicher Bruch beim Polyester und Polystyrol l?uft parallel mit einer konstanten Zugfestigkeit auch bei kürzesten Beanspruchungszeiten, w?hrend die spr?den Brüche von bei normalen Beanspruchungszeiten plastisch verformbaren Substanzen parallel laufen mit einem zum Teil sehr starken Anstieg der Zugfestigkeit, wie das beim Polyamid und Polyvinylchlorid der Fall ist. Vorgetragen auf der Arbeitssitzung des Fachausschusses „Physik der Hochpolymeren“ im Verband der Deutschen Physikalischen Gesellschaften zur Physikertagung München am 7. September 1956. Abschliegend sei noch den Herren Dr. H. Elsner und Dr. E. Nümann, Dynamit-Actien-Gesellsehafg, Troisdorf, für die freundliehe Ungerstützung dureh Hinweise gedankt. Ebenso sei noehmals dankend erw?hnt, da? die Farbenfabriken Bayer, Abt. Kautsehuk und Kunstsgoffe, freundlieherweise Kunststoffproben zur Verfügung gestellg haben.     

Fluorous synthesis of minor groove binding agents related to distamycin

Minor groove binding agents related to distamycin have been shown to target specific DNA sequences with high affinity. We report a new method for the preparation of these agents using fluorous synthesis in which the fluorous tag is located on what will become the cationic tail of the molecule. We demonstrate that fluorous synthesis yields both simple and complex polyamides in good yields and in high purity.     

Studies of the thermal degradation of acetaminophen using a conventional HPLC approach and electrospray ionization-mass spectrometry

The thermal degradation of acetaminophen is studied via conventional accelerated aging studies by initially thermally stressing the compound at temperatures between 160 degrees C and 190 degrees C and measuring the rate of decomposition by reversed-phase high-performance liquid chromatography. Rates of decomposition of the compound in the dry state and the activation energy for the process are determined and compared with previously published kinetic and thermodynamic data for the degradation of acetaminophen in solution. In addition, the thermal fragmentation of acetaminophen under electrospray ionization (ESI) conditions using an interface with a heated capillary inlet is studied and the apparent activation energy for this process also is characterized. A comparison of the data shows that acetaminophen is significantly more stable in the dry state than in solution. However, the gas-phase fragmentation of acetaminophen under ESI conditions occurs more readily than either dry- or solution-state degradation. Although the resulting electrospray fragmentation mimics the breakdown product that is formed when the compound undergoes either acid or base catalyzed hydrolysis in aqueous solutions, the mechanism that produces the fragment ion appears to involve a two-step process. Initially, the parent ion forms of the analyte are produced in the spray region of the interface followed by wall-catalyzed decomposition and re-ionization in the heated inlet capillary of the spectrometer.     

Synthesis of Sybstituted Isoxazoles and Pyrazoles Based on 1-Aryl-3,4,4-trichloro-3-buten-1-ones

3-Aryl-5-methylenehydroxyiminoisoxazoles were synthesized by reaction of 1-aryl-3,4,4-trichloro-3-buten-1-ones with hydroxylamine. Reactions of ketones with hydrazine provided pyrazole structures; therewith two pyrazole molecules underwent coupling affording 3-arylpyrazole-5-carbaldehyde azines.     

Molecular dynamics simulations of the mononuclear zinc-beta-lactamase from Bacillus cereus complexed with benzylpenicillin and a quantum chemical study of the reaction mechanism

Herein, we present results from MD simulations of the Michaelis complex formed between the B. cereus zinc-beta-lactamase enzyme and benzylpenicillin. The structural and dynamical effects induced by substrate-binding, the specific role of the conserved residues, and the near attack conformers of the Michaelis complex are discussed. Quantum chemical methods (HF/6-31G* and B3LYP/6-31G*) are also applied to study the hydrolysis reaction of N-methylazetidinone catalyzed by a monozinc system consisting of the side chains of the histidine residues (His86, His88, and His149) complexed with Zn-OH and the side chains of Asp90 and His210. From this model system, we built molecular-mechanics representations of the prereactive complex and transition state configurations docked into the active site. Linear-scaling semiempirical calculations coupled with a continuum solvent model were then performed on these static models. We propose that the experimental rate data for the B. cereus enzyme is compatible with a one-step mechanism for the hydrolysis of beta-lactam substrates in which His210 acts as a proton donor.     

Potential acting on the trapped electron

If the absorption of a trapped electron can be shown to correspond to bound—free transitions, it should be possible to calculate the potential acting on the trapped electron inversely from its absorption spectrum. In this paper we present the method of calculating the potential acting on a trapped electron from the observed absorption spectrum.     

Untersuchungen über die Oxydation von Butylbenzol in flüssiger Phase in Gegenwart von Kobalt- und Mangansalzen der Pyridincarbonsäuren

Zusammenfassung Es wurde der Einfluß der Kobalt- und Mangansalze der -, - und -Pyridincarbonsäuren auf die Luftoxydation von Rutylbenzol in flüssiger Phase untersucht. Dabei wurde festgestellt, daß das Kobaltpicolinat, Manganisonicotinat und Kobaltisonicotinat den Oxydationsverlauf zur Bildung von Carbonylverbindungen und Säuren lenken. Das Manganpicolinat weist ein selektives Oxydationsvermögen auf, vorwiegend zur Bildung von Estern.

---

Liquid phase oxidation of butyl-benzene in presence of Co and Mn pyridine carboxylates

The influence of Co- and Mn-salts of -, - and -pyridinecarboxylic acids, resp., on the oxidation of butylbenzene by air has been studied. It has been found that the Co salt of picolinic acid, Mn and Co isonicotinate direct the oxidation process in favour of carbonyl compounds and acids. With the Mn salt of picolinic acid, the oxidation mainly gives esters.

---

---

Mit 5 Abbildungen