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91.
Hooper J Sauer EL Arns S Woo TK Barriault L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(47):14124-14130
We report herein a detailed investigation into the reaction mechanism for a sequential oxy-Cope/ene reaction under anionic conditions. With DFT calculations and ab initio molecular dynamics simulations, the observed diastereoselectivity is shown to be the result of an isomerization of the enolate olefin, which would evidently not occur under neutral conditions. The potential energy surface was thoroughly mapped out for the reaction pathways and the proposed mechanism confirmed the different product distributions observed under neutral and anionic oxy-Cope conditions. In addition, other possible pathways are shown to be higher in energy and experimental evidence is given that supports the olefin-isomerization pathway. 相似文献
92.
Round robin tests have revealed the trend that the concentration of stabilizers in polyolefins is usually underestimated. However, it is still unclear whether this underestimation is due to systematic errors of the analysis procedures or to degradation of the stabilizers during the production of the round robin sample itself. Within the present work, the degradation pathways of six common antioxidants (ADK Stab AO-60, Everfos 168, Kinox 30, Irganox 3114, Irganox 1076, and Cyanox 1790) were investigated. Methods based on high-performance liquid chromatography with UV detection or hyphenated with mass spectrometry (employing either an ion trap or a quadrupole/time-of-flight instrument) were developed, whereby the suitability of atmospheric pressure photoionisation was studied and compared with the performance of more established ionisation techniques like electrospray ionisation and atmospheric pressure chemical ionisation. While ADK Stab, Kinox 30, Everfos 168, and Irganox 1076 turned out to be thermally stable at 115 °C, Irganox 3114 and Cyanox 1790 were partly degraded by oxidation. In the presence of talcum, which is a widely used inorganic filler for polyolefins, additional degradation reactions such as the cleavage of ester bonds and the loss of tert-butyl groups were observed at elevated temperature. 相似文献
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Yury Yu. Rusakov Leonid B. Krivdin Stephan P. A. Sauer Ekaterina P. Levanova Galina G. Levkovskaya 《Magnetic resonance in chemistry : MRC》2010,48(1):44-52
Experimental measurements and second‐order polarization propagator approach (SOPPA) calculations of 77Se? 1H spin–spin coupling constants together with theoretical energy‐based conformational analysis in the series of 2‐substituted selenophenes have been carried out. A new basis set optimized for the calculation of 77Se? 1H spin–spin coupling constants has been introduced by extending the aug‐cc‐pVTZ‐J basis for selenium. Most of the spin–spin coupling constants under study, especially vicinal 77Se? 1H couplings, demonstrated a remarkable stereochemical behavior with respect to the internal rotation of the substituent in the 2‐position of the selenophene ring, which is of major importance in the stereochemical studies of the related organoselenium compounds. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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A ‘catch and release’ two-step one-pot protocol has been developed for the facile and practical synthesis of substituted guanidines from thioureas and various amines utilizing readily available brominated polystyrene resin. 相似文献
99.
Wavelets for multichannel signals 总被引:1,自引:0,他引:1
In this paper, we introduce and investigate multichannel wavelets, which are wavelets for vector fields, based on the concept of full rank subdivision operators. We prove that, like in the scalar and multiwavelet case, the existence of a scaling function with orthogonal integer translates guarantees the existence of a wavelet function, also with orthonormal integer translates. In this context, however, scaling functions as well as wavelets turn out to be matrix-valued functions. 相似文献
100.
A. Sauer 《Archiv der Mathematik》2002,79(3):182-187
We prove that if a transcendental meromorphic function has no Julia direction and is bounded on a path to ¥ \infty then there is a common Julia direction for all derivatives. Related statements are obtained under the assumption that f is o(?{ | z | }) o(\sqrt{\mid z \mid}) or O(?{ | z | }) O(\sqrt{\mid z \mid}) on a path to ¥ \infty . Further we disprove a conjecture of Frank and Wang by means of a counterexample. 相似文献