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1.
Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters 下载免费PDF全文
Maria Camila Blanco Jaimes Alexander Ahrens Daniel Pflästerer Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):427-433
Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact. 相似文献
2.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
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In this article, we present results of an empirical study with 500 German students of grades 7 and 8. The study focussed on students' mathematics achievement and their interest in mathematics as well as on the relation between these two constructs. In particular, the results show that the development of an individual student's achievement between grade 7 and grade 8 depends on the achievement level of the specific classroom and therefore on the specific mathematics instruction Interest in mathematics could be regarded a predictor for mathematics achievement Moreover, our findings suggest that the students show hardly any fear of mathematics independent of their achievement level. 相似文献
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C. Andreoiu D. Rudolph I. Ragnarsson C. Fahlander R.A.E. Austin M.P. Carpenter R.M. Clark J. Ekman R.V.F. Janssens T.L. Khoo F.G. Kondev T. Lauritsen T. Rodinger D.G. Sarantites D. Seweryniak T. Steinhardt C.E. Svensson O. Thelen J.C. Waddington 《The European Physical Journal A - Hadrons and Nuclei》2002,14(3):317-348
High-spin states in 59Cu were populated using the fusion-evaporation reaction 28Si + 40Ca at a beam energy of 122 MeV. The Gammasphere Ge-detector array in conjunction with the 4π charged-particle detector array
Microball allowed for the detection of γ-rays in coincidence with evaporated light particles. The resulting extensive high-spin
decay scheme of 59Cu is presented, which comprises more than 320 γ-ray transitions connecting about 150 excited states. Their spins and parities
have been assigned via directional correlations of γ-rays emitted from oriented states. Average quadrupole moments of rotational
bands have been determined from the analysis of residual Doppler shifts. Shell model calculations in the fp shell are invoked to study some of the low-spin states, while the experimental characteristics of the rotational bands are
analyzed in the configuration-dependent cranked Nilsson-Strutinsky (CNS) approach.
Received: 15 February 2002 / Accepted: 23 April 2002 相似文献
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Masaaki Kubota Raul A. Reimer Kuniko Terajima Yuji Yoshimura Akio Nishijima 《Analytica chimica acta》1987
Inductively-coupled plasma/atomic emission spectrometry with a high-resolution vacuum scanning monochromator is described for the determination of sulfur at 180.734 nm. The behavior of the signal-to-background ratio is investigated as functions of RF power, argon gas flow rate and observation height above the load coil. Under the operating conditions selected, the detection limit is 3 μg l?1. The Se I 196.090-nm line is chosen as internal standard, because the S/Se line pair exhibited the least change with carrier gas flow rate and acid concentration of solution. Sulfur in NiMo and CoMo/ Al2O3 catalysts used for coal liquefaction is determined as S(II) and S(VI) species. The total amount of the species agreed well with the sulfur value obtained by the conventinal combustion method. 相似文献
10.
From the highly refined proton-NMR spectra of monocyclic and bicyclic aminopolyethers, signal shifts have been observed which indicate conformation changes in the ligand moiety. Their dependence on solvent, coordinated cation and anion is discussed, and an interpretation of the spectra is put forward on the basis of dynamic symmetry patterns. 相似文献