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211.
Joachim G. Liehr Gareth A. Brenton John H. Beynon James A. McCloskey Wolfgang Blum Wilhelm J. Richter 《Helvetica chimica acta》1981,64(3):835-843
In isobutane chemical ionization mass spectrometry benzyl alcohol exhibits ions at m/z 147 (‘M + 39’) that arise by a loss of H2O from [M + C4H9]+, i.e. ‘M + 57’ complex ions. Electrophilic aromatic substitution of a proton at an ortho-position of neutral C6H5CH2OH with [t-C4H9]+ and, alternatively, nucleophilic substitution of H2O at the benzylic carbon in \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm C_6 H_5 CH_2}\mathop {\rm O}\limits^+ {\rm H}_2 $\end{document} with CH2?C (CH3)2 are discussed as possible pathways. Evidence in favor of the latter is derived from the analysis of C6D5CH2OH and C6H5CD2OH for the origin of the H-atoms lost in H2O. The inferred ion structure of m/z 147 is verified by mass-analyzed ion kinetic energy (MIKE.) measurements of its collision-activated (CA.) decomposition. MIKE./CA. spectra of mass-selected m/z 147 ions, once generated by (CI(i-C4H10) from benzyl alcohol and, once, from 2-methyl-4-phenyl-2-butanol match closely and, thus, reflect identical ion structures. With reference to the simple genesis of this ion from the latter precursor, the structure in question can be concluded to be \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm C_6 H_5 CH_2 CH_2}\mathop {\rm C}\limits^+ ({\rm CH}_3)_2 $\end{document} . 相似文献
212.
Bernd Reif Valentin Wittmann Harald Schwalbe Christian Griesinger Karlheinz Wrner Kerstin Jahn-Hofmann Joachim W. Engels Wolfgang Bermel 《Helvetica chimica acta》1997,80(6):1952-1971
1-(2′-Deoxy-2′-fluororibofuranosyl)pyrimidines were synthesized and incorporated into an RNA oligonucleotide to give 5′-r[CfGCf(UfUfCfG)GCfG]-3′ (Cf: short form of C = 2′-deoxy-2′-fluorocytidine; Uf: short form of U = 2′-deoxy-2′-fluorouridine). The oligomer was investigated by means of UV, CD, and NMR spectroscopy to address the question of how F-labels can substitute 13C-labels in the ribose ring. Through-space (NOE) and through-bond (scalar couplings) experiments were performed that make use of the ameliorated chemical-shift dispersion induced by 19F as an alternative heteronucleus. A comparison of the structures of fluorinated vs. unmodified oligomer is given. It turns out that the fluorinated oligonucleotide exists in a 14:3 equilibrium between a hairpin and a duplex conformation, in contrast to the unmodified oligonucleotide which predominantly adopts the hairpin conformation. Furthermore, the fluorinated hairpin structure adopts two distinct conformations that differ in the sugar conformation of the U and C nucleoside units, as detected by the 19F-NMR chemical shifts. The role of the 2′-OH group as stabilizing element in RNA secondary structure is discussed. 相似文献
213.
Peter A. Beaven Mauro Marmotti Reinhard Kampmann Joachim Knoth Heinrich Schwenke 《Spectrochimica Acta Part B: Atomic Spectroscopy》2003,58(12):2049-2057
A multi-wire, gas-filled position-sensitive detector has been developed for the simultaneous recording of wavelength-dispersed X-ray signals that enables X-ray fluorescence spectrometry with a limited multi-element capability in the low Z element range. Details of the modular construction of the detector are given. The detector performance was characterized using Al–K radiation and a variable slit system. The detector has been applied in a laboratory spectrometer equipped with an electron source and a double multilayer mirror device as the wavelength-dispersing element. Spectra from Al and Si obtained in the simultaneous acquisition mode show good agreement with calculations performed using a ray-tracing model. 相似文献
214.
Cycloprop [a] acenaphthylene was found to rearrange to phenalene in the presence of rhodium dicarbonyl chloride dimer. Deuterium labeling of this molecule at C(7) (both exo and endo), at C(8), at C(7) (exo) and C(8) and at C(7) (exo), C(8), and C(8') indicated that the C(7) (exo) deuterium was migrating stereospecifically. Furthermore, all of the isotopic label present in the cycloprop[a]acenaphthylene was found statistically distributed over positions 1, 3, 4, 6, 7, and 9 of the phenalene product. Control experiments established the need of the catalyst, the inability to achieve rearrangement of the exo-7-methyl derivative, and the susceptibility of a monodeuterated phenalene for extensive isotopic scrambling in its own right when exposed to rhodium(I). These results have been interpreted on the basis of oxidative addition by rhodium(I) into the central bond of cycloprop[a]acenaphthylene from above the “flap”, followed by shifting of the C(7) (exo) hydrogen (or deuterium) to give a η3-allylrhodim-(III) complex. The experimental data further support a mechanism involving subsequent rearrangement of this intermediate around the periphery of the phenalene ring. This process which is otherwise degenerate is thought to be facilitated by the special electronic features of the phenalenyl system. 相似文献
215.
We investigate several classes of inequalities for the symmetric travelling salesman problem with respect to their facet-defining properties for the associated polytope. A new class of inequalities called comb inequalities is derived and their number shown to grow much faster with the number of cities than the exponentially growing number of subtour-elimination constraints. The dimension of the travelling salesman polytope is calculated and several inequalities are shown to define facets of the polytope. In part II (On the travelling salesman problem II: Lifting theorems and facets) we prove that all subtour-elimination and all comb inequalities define facets of the symmetric travelling salesman polytope. 相似文献
216.
H. S. P. Grässer 《Aequationes Mathematicae》1976,14(3):363-386
Notation Throughout this paper Greek indices, , , and Latin indicesi, j, h, k, assume the values 1, ,m, and 1, ,n respectively. The summation convention is operative in respect of both sets of indices.This work was supported by the South African Council for Scientific and Industrial Research.At time of writing Professor Grässer was Visiting Scholar at the University of Arizona, Tucson, Arizona. 相似文献
217.
218.
Markus Follmann Nils Griebenow Michael G. Hahn Ingo Hartung Franz‐Josef Mais Joachim Mittendorf Martina Schfer Hartmut Schirok Johannes‐Peter Stasch Friederike Stoll Alexander Straub Peter Jeschke Ralf Nauen Michael Edmund Beck Hans‐Wilhelm Engels Hans‐Georg Pirkl Reinhard Albers Rolf W. Albach Jens Krause Andreas Hoffmann Holger Casselmann Jeff Dormish 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(36):9503-9503
219.
G. Grätzer 《Algebra Universalis》2013,69(4):301-304
In a recent paper, G. Czédli and E. T. Schmidt present a structure theorem for planar semimodular lattices. In this note, we present an alternative proof. 相似文献
220.
Tetiana Krachko Mark Bispinghoff Dr. Aaron M. Tondreau Dr. Daniel Stein Matthew Baker Dr. Andreas W. Ehlers Prof. Dr. J. Chris Slootweg Prof. Dr. Hansjörg Grützmacher 《Angewandte Chemie (International ed. in English)》2017,56(27):7948-7951
Phosphinidenes [R-P] are convenient P1 building blocks for the synthesis of a plethora of organophosphorus compounds. Thus far, transition-metal-complexed phosphinidenes have been used for their singlet ground-state reactivity to promote selective addition and insertion reactions. One disadvantage of this approach is that after transfer of the P1 moiety to the substrate, a challenging demetallation step is required to provide the free phosphine. We report a simple method that enables the Lewis acid promoted transfer of phenylphosphinidene, [PhP], from NHC=PPh adducts (NHC=N-heterocyclic carbene) to various substrates to produce directly uncoordinated phosphorus heterocycles that are difficult to obtain otherwise. 相似文献