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1.
Winfried Wagner-Redeker Karsten Levsen Helmut Schwarz Waltraud Zummack 《Journal of mass spectrometry : JMS》1981,16(8):361-371
Using the relative abundance of metastable ions, collisional activation spectra, field ionization kinetic measurements, isotopic labelling, appearance energy and kinetic energy release data, it is shown that linear alkyne radical cations with more than six carbon atoms do not isomerize to equilibrating structures prior to decomposition. At the shortest ion lifetimes the molecular ions of linear alkynes decompose mainly by simple β-bond fission which allows an unequivocal localization of the triple bond. At medium ion lifetimes fragmentation occurs predominantly via a McLafferty rearrangement, while at long ion lifetimes competing alkyl losses prevail. These alkyl losses occur via cyclic intermediates leading to thermochemically stable cycloalkenyl ions. All these reactions occur with a high specificity with respect to the carbon and hydrogen atoms involved and are preceded by little or no hydrogen exchange reactions. 相似文献
2.
Gerhard Buchbauer Waltraud Pernold Dorothea Rassl Brigitte Blach 《Monatshefte für Chemie / Chemical Monthly》1981,112(4):517-527
The synthesis of some new potentially, nitrogenefree spasmolytics is described. Formally the benzene nucleus in some mandelic acid esters, known by their mild spasmolytic activity, is substituted for the isocamphane bicyclus by a) SeO2 oxidation of 1-(3,3-Dimethyl-2-exo-norbornyl)-ethanone (5) to the corresponding ketoaldehyde6, b) oxidation of6 to the isocamphane analogous mandelic acid4 and c) esterification of derivatives of4 with isoamylalcohol and benzylalcohol. Attemps to dehydrate the methylester7 to camphenylideneacetic acid methylester (12) by various methods failed, probably because of the ring strain.
Teil der Diplomarbeit vonB. Blach, Universität Wien 1981. 相似文献
3.
The synthesis of yomogi alcohol (2, 5, 5-trimethylhepta-3,6-dien-2-ol, 2 ) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out. Acidic reagents open the ring of yomogi alcohol epoxide ( 16 ) at with participation of the 6,7-double-bond, a shift of the vinyl group results to yield a compound with the santolinyl skeleton. The same reagents are without effect when this double bond reduced. Action of butyllithium of the benzaldehyde acetal ( 41 ) of 2, 5-dimethyl-4-vinyl-2, dihydroxy-hex-5-ene ( 28 ), obtained by acid-catalyzed ring opening of yomogi alcohol epoxide in the presence of benzaldehyde, leads to santolinatriene ( 42 ). This vinyl shift is not observed in the case of O-acetyl yomogi alcohol epoxide ( 46 ), from white a compound believed to be an oxetan 48 (R ? COCH3) is formed with concomitent shift of the acetate group. Further unusual reactions of the oxetan are described, and some observation about the epoxidation of sterically hindered allyl alcohols and their acetates are made. 相似文献
4.
The reaction of linear (Si(n)Cl(2)(n)(+2); n = 3-5) and cyclic (Si(5)Cl(10)) perchloropolysilanes with 1 or 2 equiv of LiN(SiMe(3))(2) results in the formation of the bis(trimethylsilyl)amino derivatives (Me(3)Si)(2)NSi(3)Cl(7) (1), (Me(3)Si)(2)NSi(4)Cl(9) (2), (Me(3)Si)(2)N(SiCl(2))(n)N(SiMe(3))(2) (n = 3, 4; n = 4, 5; n = 5, 6), cyclo-(Me(3)Si)(2)NSi(5)Cl(9) (7), and cyclo-[(Me(3)Si)(2)N](2)Si(5)Cl(8) (8). 1-8 easily can be hydrogenated with LiAlH(4) to give the corresponding amino and diamino polysilanyl hydrides. The monosubstituted and cyclic compounds 1, 2, 7, and 8 additionally afford Si-Si bond scission products, which cannot be separated in all cases. Chloro- and dichloro derivatives of Si(3)H(8), n-Si(4)H(10), and n-Si(5)H(12) are obtained from the corresponding aminosilanes and dry HCl. All compounds were characterized by standard spectroscopic techniques. For Si-H derivatives the coupled (29)Si NMR spectra were analyzed to obtain an unequivocal structural proof. 相似文献
5.
Waltraud Kahle 《商业与工业应用随机模型》2019,35(2):211-220
We consider a Wiener process with linear drift for degradation modeling. Regularly, maintenance actions are carried out which produce a reduction of the degradation level. In this paper, we consider the influence of such maintenance actions to the further development of the degradation process and the resulting lifetime distribution. A connection between virtual age in Kijima‐type models and degradation level in the underlying degradation process is developed. Furthermore, estimators for the process parameters as well as for the degree of repair are developed. 相似文献
6.
M. Arif Hasan Shinhu Cho Kevin Remick Alexander F. Vakakis D. Michael McFarland Waltraud M. Kriven 《International Journal of Solids and Structures》2013,50(20-21):3207-3224
We present an experimental study of primary pulse transmission in coupled ordered steel granular chains embedded in poly-di-methyl-siloxane (PDMS) elastic matrix. Two granular one-dimensional chains are considered (an ‘excited’ and an ‘absorbing’ one), each composed of 11 identical steel beads of 9.5 mm diameter with the centerline of the chain spaced at fixed distances of 0.5, 1.5 or 2.5 mm apart. We directly force one of the chains (the excited one) by a transient pulse and measure, by means of laser vibrometry, the primary transmitted pulses at the end beads of both chains and at the first bead of the absorbing chain. It is well known that the dynamics of this type of ordered granular media is strongly nonlinear due, (i) to Hertzian interactions between adjacent beads, and (ii) to possible bead separations in the absence of compressive forces and ensuing collisions between neighboring beads. Accordingly, we develop a strongly nonlinear theoretical model that takes into account the coupling of the granular chains due to the PDMS matrix, with the aim to model primary pulse transmission in this system. After validating the model with experimental measurements, we employ it in a predictive fashion to estimate energy transfer between chains as a function of the interspatial distance between chains. Furthermore, based on this model we perform predictive matrix design to achieve maximum energy transfer from the excited to the absorbing chain, and provide a theoretical explanation of the nonlinear dynamics governing energy transfer (including energy equi-partition) in this system. 相似文献
7.
Anna Edelsbacher Ernst Urban Waltraud Weidenauer 《Monatshefte für Chemie / Chemical Monthly》1992,123(8-9):741-747
Summary Optically pure available lactones1 and5 were diastereoselectively oxidised tocis-diols2 and6 by KMnO4 and to epoxides3 and7 by 3-chloroperoxybenzoic acid. Epoxide3 was cleaved totrans-diol4, whereas hydrolysis of7 afforded tricyclic carboxylic acid8. Optic ally puredihydroxylactones2,4, and6 are valuable models for structure determination of the antimicrobial garlic component garlicin.
Synthese enantiomerenreiner 5,6-Dihydroxy-isobenzofuranone und 5,6-Dihydroxy-4,7-methano-isobenzofuranone
Zusammenfassung Die in enatiomerenreiner Form verfügbaren Lactone1 und5 wurden durch diastereoselektive Oxidation mit KMnO4 zu dencis-Diolen2 und6 bzw. mit 3-Chlorperoxybenzoesäure zu den Epoxiden3 und7 umgesetzt. Das Epoxid3 liefert bei der Hydrolyse dastrans-Diol4, während aus7 die tricyclische Carbonsäure8 entsteht. Die optisch reinen Dihydroxylactone2,4 und6 können als Vergleichssubstanzen zur Strukturaufklärung des antimikrobiellen Knoblauchinhaltsstoffes Garlicin dienen.相似文献
8.
Global Optimization by Multilevel Coordinate Search 总被引:3,自引:0,他引:3
Inspired by a method by Jones et al. (1993), we present a global optimization algorithm based on multilevel coordinate search. It is guaranteed to converge if the function is continuous in the neighborhood of a global minimizer. By starting a local search from certain good points, an improved convergence result is obtained. We discuss implementation details and give some numerical results. 相似文献
9.
In exploring versatile synthetic routes to (E)-allylamine derivatives with antimycotic properties, a new method has been found in the trans-reduction of tertiary 2-alkinylanunes by diisobutylaluminum hydride (DIBAH). The stereoselectivity of this reaction, which is in contrast to the well-known cis-hydroalumination of disubstituted alkynes, and the regioselectivity have been studied in detail. Tertiary 2-alkinylamines 1 were generally reduced to (E)-2-alkenylamines 2 in toluene at 40°, and tertiary 2,4-alkadiynylamines 3 yielded a mixture of(E)-2-alken-4-ynylamines 4 and 2(E),4(Z)-alkadienylamines 5 in high stereochemical purity. This reduction was clearly different with respect to reactivity and selectivity in comparison with other reactions also proceeding via trans-hydroalumination, namely the lithium aluminum hydride reduction of α-hydroxyacetylenes and the reaction of alkynes with LiAlH(iso-Bu)2(n-Bu). Tertiary 6-hydroxy-2, 4-alkadiynylamines 10 were reduced to 6-hydroxy-2(E)-alken-4-ynylamines 11 with diisobutylaluminum hydride, whereas on treatment with lithium aluminum hydride 6-hydroxy-4(E)-alken-2-ynylamines 12 were obtained. LiAlH (iso-Bu)2(n-Bu) did not react with 2-alkinylamine 1a and the 2,4-alkadiynylamine 3a was only monohydroaluminated without discrimination of the two acetylene groups. A possible mechanism for the diisobutylaluminum hydride reduction of 2-alkinylamines is presented. 相似文献
10.
Miriam Karni Yitzhak Apeloig Detlef Schrder Waltraud Zummack Roberto Rabezzana Helmut Schwarz 《Angewandte Chemie (International ed. in English)》1999,38(3):331-335
Neutralization of [C,H,Si,X] radical cations (X=F, Cl) in conjunction with electronic structure calculations provides the first experimental evidence for the formation of the neutral silynes HC≡SiF and HC≡SiCl, which have nonlinear structures (see picture). 相似文献