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1.
Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2 下载免费PDF全文
Stefan Kissling Peter T. Altenbuchner Dr. Maximilian W. Lehenmeier Dr. Eberhardt Herdtweck Dr. Peter Deglmann Dr. Uwe B. Seemann Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8148-8157
The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO2 revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO2 co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion. 相似文献
2.
A synthesis of methyl 2-oxo-5-vinyl-tetrahydrofuran-3-carboxylate involving five synthetic steps from commercially available 3,4-dihydroxybutene is reported. 相似文献
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Waldemar Iwanek 《Tetrahedron: Asymmetry》1998,9(24):146-4290
A method for the preparation of a single diastereomer of the oxazine derivative of calixresorc[4]arene 3 has been developed. Lewis acids were employed for opening of the oxazine ring. 相似文献
8.
Saito H Sivaguru J Jockusch S Inoue Y Adam W Turro NJ 《Chemical communications (Cambridge, England)》2005,(27):3424-3426
Oxazolidinone-functionalized enecarbamates undergo diastereoselective E/Z photoisomerization upon direct and triplet sensitized irradiations with chiral/achiral sensitizers, showing that the enhanced product diastereoselectivity depends on the solvent and temperature. 相似文献
9.
Waldemar Gottardi 《Mikrochimica acta》1982,77(5-6):371-386
Zusammenfassung Zwischen dem Redoxpotential und dem log der Jodkonzentration jodidhaltiger wäßriger Lösungen
besteht unabhängig vom pH-Wert über 3–4 Zehnerpotenzen ein weitgehend linearer Zusammenhang, der eine einfache und genaue quantitative Bestimmung von Jod ermöglicht. Da unter diesen Bedingungen sehr viele Oxydationsmittel äußerst rasch und quantitativ unter Bildung von Jod (bzw. Trijodid) reagieren, kann die Methode sehr vielseitig angewandt werden (z. B. zur Bestimmung von Chlor, Brom, O- und N-Halogenverbindungen, Ozon u. a.).Die Leistungsfähigkeit der Methode ist vor allem gekennzeichnet durch die rasche Redoxpotentialeinstellung in jodidhalügen Jodlösungen, die absolute Konstanz der als Meßelektrode dienenden Platinelektrode, die unter sorgfältiger Einhaltung der gewählten Meßbedingungen (Temperatur, Jodidkonzentration, Gesamtionenstärke) eine Nacheichung praktisch nicht notwendig macht, sowie die Möglichkeit, mit den gleichen Reagenzien den Konzentrationsbereich 10–1–2,5×10–8
M/l zu vermessen. Mit den relativen Standardabweichungen 0,7–1,2% im Bereich 10–3–10–5
M/l, 1,5–1,7% bei 10–6
M/l bzw. 4,4–9,1% bei 10–7
M/l stellt die potentiometrische Jodbestimmung eines der genauesten analytischen Verfahren im Bereich niederer Konzentrationen dar, das zudem durch einen äußerst geringen meßtechnischen Aufwand gekennzeichnet ist.
The potentiometric determination of iodine and iodine releasing oxidants
Summary Between the redox potential and the log of the iodine concentration of aqueous iodine solutions (pH<9) containing an excess amount of iodide exists independent of the pH-value over a concentration range of 3–4 powers a nearly linear relation, which enables a simple and precise determination of iodine. Since under these conditions a great many oxidants react very fast and quantitatively forming iodine (resp. tri-iodide) the method can be used very versatile (e. g. for the determination of chlorine, bromine, O- and N-halogene compounds, ozone). The efficiency of the method is characterized above all by the fast adjustment of the redox potential in iodine solutions containing iodide, the constancy of the Pt-electrode, by which carefully observing the choosen measuring conditions (temperature, iodide concentration, total ionic strength) a recalibration is virtually unnecessary, and the possibility to measure with the very same reagents the concentration range 10–1–2.5×10–8 M/l. With relative standard deviations of 0.7–1.2% in the range 10–3–10–5 M/l, 1.5–1.7% at 10–6 M/l resp. 4.4–9.1% at 10–7 M/l the potentiometric determination of iodine, though requiring only a very simple instrumental fitting out, represents one of the most precise analytical methods at low concentration levels.相似文献
10.
J. Sivaguru Hideaki Saito Thomas Poon Waldemar Adam Yoshihisa Inoue Nicholas J. Turro 《Tetrahedron》2006,62(28):6707-6717
On photooxygenation (methylene blue as sensitizer) of E/Z enecarbamates, equipped with the oxazolidinone chiral auxiliary, the oxidative cleavage of the alkenyl functionality releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense (R vs S) of the stereoselectivity in the MDB formation depends on the choice of the alkene configuration; the efficacy of stereocontrol may be tuned by appropriate solvent and temperature conditions. Highlighted is the finding that the formation of the preferred MDB enantiomer (R or S) depends for the E isomer on the chosen solvent and temperature, but not for the corresponding Z isomer. The activation parameters for the various solvents disclose that differential entropy effects (ΔΔS‡) dominate the conformationally more flexible E diastereomers. As mechanistic rationale for this unprecedented conformationally imposed stereochemical behavior, we propose the competitive action of stereoselective vibrational quenching of the attacking singlet oxygen by the enecarbamate versus sterically controlled stereoselective oxidative cleavage of its double bond. 相似文献