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101.
Anne-Marie Caminade Fayez El Khatib Antoine Baceiredo Max Koenig 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2-4):365-367
Abstract The ozonization of various halophosphines 1a-j leads with quantitative yields to the corresponding phosphine oxides 2a-j. Ozonization is a convenient method of oxidation, in particular of compounds with bulky ligands (1c, 1d, 1e). 相似文献
102.
David G. Cameron Harry R. Hudson Isaac A. O. Ojo Max Pianka 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):183-197
Abstract N-(ω-Aminoalkyl)- and N-(ω-guanidinoalkyl)-aminoalkanephosphonic acids have been prepared from α, ω-diaminoalkanes by reaction with chloromethanephosphonic acid (or an ester of a halogeno-alkanephosphonic acid), followed by treatment with S-methylisothiouronium chloride. Ethylene diamine yielded 1-phosphonomethyl-2-iminoimidazolidine. A number of 1:1 salts of the α, ω-diamines and chloromethanephosphonic acid are also reported. Doubly charged zwitterionic structures are assigned to both ω-amino and ω-guanidino compounds on the basis of 31P and 13C nmr data. Thus the addition of an excess of acid (D2SO4) causes the 31P chemical shift to move to higher field, from ca. 8 to 14 ppm, whilst 1 Jpc increases from ca. 130 to 150 Hz. The 1H and 13C chemical shifts of the terminal methylene groups in the polymethylene chain are unaffected by acidification. Fast atom bombardment mass spectrometry gives rise to characteristic [M + H]+ ions, frequently as the base peak, and to fragmentations involving the loss of phosphorous acid, or the formation of ions resulting from carbon-nitrogen or carbon-carbon cleavage. The compounds show activity against a number of fungal pathogens and other microbial organisms. 相似文献
103.
Dr. Max Bielitza Prof. Dr. Jörg Pietruszka 《Angewandte Chemie (International ed. in English)》2013,52(42):10960-10985
Psymberin is a marine natural product which has attracted a great deal of interest since its isolation: While the highly cytotoxic compound was detected early on as an ingredient in a marine sponge, it took over a decade and 600 additional samples for the structure to eventually be assigned. In the last eight years fascinating synthetic and biosynthetic investigations have led to a more detailed understanding as well as a new starting point for structure–activity studies towards new antitumor compounds. The Review gives an in‐depth insight into the progress in the field of the marine polyketide psymberin and demonstrates how organic synthesis is influencing neighboring scientific subjects. 相似文献
104.
A methodology for kinetic modeling of conversion processes is presented.The proposed approach allows to overcome the lack of molecular detail of the petroleum fractions and to simulate the reactions of the process by means of a two-step procedure.In the first step,a synthetic mixture of molecules representing the feedstock is generated via a molecular reconstruction method,termed SR-REM molecular reconstruction.In the second step,a kinetic Monte Carlo method,termed stochastic simulation algorithm(SSA),is used to simulate the effect of the conversion reactions on the mixture of molecules.The resulting methodology is applied to the Athabasca vacuum residue hydrocracking.An adequate molecular representation of the vacuum residue is obtained using the SR-REM algorithm.The reaction simulations present a good agreement with the laboratory data for Athabasca vacuum residue conversion.In addition,the proposed methodology provides the molecular detail of the vacuum residue conversion throughout the reactions simulations. 相似文献
105.
Dr. Matthias Lein Dr. Linbin Jiang Dr. Wanxing Wei Prof. Dr. Jianyi Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14126-14142
The mechanism of CuI‐catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2Cu]? prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α‐ or γ‐selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α‐ and γ‐substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α‐ and γ‐substituted products are 2.75 kcal mol?1 with SPO(OiPr)2, 2.44 kcal mol?1 with SPiv, 2.33 kcal mol?1 with OPiv, and 1.98 kcal mol?1 with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2>SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2, SPiv, OPiv, and Cl groups on the Cu group. 相似文献
106.
Model order reduction (MOR) techniques that project onto a general subspace are common practice. In Elastic Multi-Body-Dynamics (EMBD) distinct interface coordinates are required for the interconnection of the elastic structure and the multi-body system. For that reason, a physical interpretation of the coordinates is mandatory, which is not the case for reduced order models in a general subspace. To make alternative MOR techniques accessible for EMBD, a back-projection approach was introduced by [1]. Therein, the system is projected back onto the physical configuration space, which requires the inversion of the master partition of the projection matrix. But the procedure lacks of robustness and generality. A novel approach is introduced by generating additional master coordinates using sensor placement methods, e.g. the Effective-Independence-algorithm (EfI) [2]. By using a rank criterion for the automatic selection of additional coordinates, the improved back-transformation performs properly and without damaging the reduced order model at a fairly small computational overhead, which is demonstrated at the example of a gear box housing. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
107.
Composition of oxygen precipitates in Czochralski silicon wafers investigated by STEM with EDX/EELS and FTIR spectroscopy
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Dawid Kot Gudrun Kissinger Markus Andreas Schubert Max Klingsporn Andreas Huber Andreas Sattler 《固体物理学:研究快报》2015,9(7):405-409
In this work, we investigated the stoichiometry of oxygen precipitates in Czochralski silicon wafers. The thickness dependence of the Cliff–Lorimer sensitivity factor for the silicon/oxygen system was determined and applied for the investigation of the stoichiometry of oxygen precipitates by EDX. The results show that both plate‐like oxygen precipitates and a transitional form between plate‐like and octahedral precipi‐ tates consist of SiO2. This was confirmed by EELS low loss spectra where the typical spectrum for amorphous SiO2 was observed. Moreover, the absorption band of plate‐like precipitates at 1227 cm–1 was found in the low temperature FTIR spectrum. It was demonstrated that this band can only be simulated by the dielectric constants of amorphous SiO2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
108.
C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations
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Dr. Torsten Bruhn Dipl.‐Chem. Franziska Witterauf Dr. Daniel C. G. Götz Carina T. Grimmer Dipl.‐Chem. Max Würtemberger Prof. Dr. Udo Radius Prof. Dr. Gerhard Bringmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3998-4006
β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins. 相似文献
109.
Max Kronenwerth Kenan A. J. Bozhüyük Dr. Astrid S. Kahnt Prof. Dr. Dieter Steinhilber Dr. Sophie Gaudriault Marcel Kaiser Prof. Dr. Helge B. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17478-17487
Six new lipodepsipeptides and an additional linear derivative named taxlllaids A–G ( 1 – 7 ) have been identified in the entomopathogenic bacterium Xenorhabdus indica. The structures of the main compounds have been solved by detailed NMR spectroscopic analysis and the structures of minor derivatives were elucidated by a combination of labelling experiments and detailed MS experiments. The absolute configuration of the taxlllaids was deduced by using the advanced Marfey method and analysis of the biosynthesis gene cluster showing the presence of epimerisation domains, which was subsequently proved to be correct by solid‐phase peptide synthesis of all taxlllaids. The exchange of a single amino acid in the adenylation domain was shown to be responsible for substrate promiscuity of the third A domain, resulting in the incorporation of leucine, phenylalanine or tyrosine. Bioactivity testing revealed the taxlllaids to be weakly active against Plasmodium falciparum and against a number of eukaryotic cell lines. 相似文献
110.
Dr. José I. Urgel Dr. Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Dr. Junzhi Liu Shantanu Mishra Dr. Qiang Sun Amogh Kinikar Dr. Roland Widmer Samuel Stolz Max Bommert Dr. Reinhard Berger Dr. Pascal Ruffieux Dr. Carlo A. Pignedoli Prof. Dr. Klaus Müllen Prof. Dr. Xinliang Feng Prof. Dr. Roman Fasel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13383-13389
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献