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A cheap synthesis of the so‐called ‘decalin‐1,8‐diones’ started with the conjugate (1,4‐) addition of cyclohex‐2‐en‐1‐one derivatives to the γ‐position of the dilithium derivative (buta‐1,3‐diene‐1,1‐bis(olate)) of crotonic acid. Hydrogenation of these ‘1,4‐γ’ adducts and final cyclization afforded the enol tautomers of decalin‐1,8‐diones. Nucleophilic substitutions at these 3‐oxoenols by NH3 or primary amines created only monoamino products (namely, 3‐oxoenamines) whose reactions with OPCl3 yielded dihydro(1,3,2)oxazaphosphinin‐2‐one derivatives. The two regioisomers of a trimethyl‐3‐oxoenamine served as models for the constitutional assignments of the two rapidly interconverting (hence, individually NMR‐invisible), tautomeric trimethyl‐3‐oxoenols. Such methyl substitutions served to break the ‘pretended’ symmetry of ‘decalin‐1,8‐dione’. Hydrazine and 3‐oxoenols furnished oxygen‐free indazole derivatives whose N?H bonds exchanged with t1/2=ca. 0.00035 s at ca. ?58(9) °C. 相似文献
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Daniel S. Covita Dimitrios F. Anagnostopoulos Hermann Fuhrmann Hubert Gorke Detlev Gotta Alexander Gruber Albert Hirtl Tomoichi Ishiwatari Paul Indelicato Thomas S. Jensen Eric-Olivier Le Bigot Valeri E. Markushin Michael Nekipelov Vladimir N. Pomerantsev Vladimir P. Popov Joaquim M. F. dos Santos Philipp Schmid Leopold M. Simons Marian Theisen Martino Trassinelli Joao F. C. A. Veloso Johann Zmeskal 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2018,72(4):72
117.
G. Brunner 《Isotopes in environmental and health studies》2013,49(9-10):328-333
Mit Berücksichtigung eines die horizontale Probeausdehnung umfassenden Geometriefaktors werden unter praktisch brauchbaren Bedingungen absolute Fluoreszens- und Streustrahlungsausbeuten für sättigungsdicke und für dünne Proben berechnet. Die aus ihnen herleitbaren Meβempfindlichkeiten zeigen, daβ sich geringe Konzentrationen von relativ leichten bis mittelschweren Elementen besonders gut messen lassen, wenn man entweder dicht oberhalb der Absorptionskanten liegenda Energien anwendel oder bei relativ hoher Anregungsenergie die Streustahlung abtrennt. Bei groβen Konzentrationen solcher Elemente kann auch ohne Streustrahlungsabtrennung mit relativ hohen Anregungsenergien gemessen werden, wobei sogar unter gewissen Bedingungen mit Zunahme der Anregungsenergie eine leichte Empfindlichkeitsverbesserung eintritt. Bei schweren Elementen ist der Gesichtspunkt der Probendicke vielfach wichtiger als die Wahl der Anregungsenergie. Für dūnne Proben lassen sich relativ recht hohe Empfindlichkeiten erzielen, was jedoch zu einem Problem der absoluten Intensitāten angesichts des Detektor-Strahlungsuntergrundes fūhren kann. 相似文献
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Hansurudolf Meier Hanspeter Kuenzi Hermann Fuhrer Günher Rist 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):537-538
Abstract The 2.4-bisfunctionalized phenol 1, a commercial antioxidant, is dehydrogenated regioselectively with potassium ferricyanide. affording the corresponding p-quinone methide 2. 1,6-Addition of nucleophiles e.g. thiols to 2 gives rise to the corresponding addition products e.g. the dithioacetals 4 of the corresponding substituted benzaldehyde. On the other hand, treatment of 2 with αα′-azoisobutyronitrile at 90°C leads to compounds 5a-b and 6, addition products of the cyanopropyl radical to the quinone methide 2. The structures of all products are confirmed mainly by 1H-NMR-and 13C-NMR-spectroscopy and the mode of their formation is discussed. 相似文献
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Ludwig Hermann 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):176-178
Abstract Human and animal excrements, in particular manure, stand for a significant and undisputable source of plant nutrients and renewable energy. In Europe, only 36% of P-inputs to soils originate from primary resources (rock phosphate) whereas 63% come from animal and human excretions applied to cropland as manure, digestion residues and sewage sludge. Simultaneously these waste flows represent a potential hazard to human health and aquatic bodies because of pathogens and eutrophication. Management of these waste flows is far from being sustainable, in part due to the lack of efficient processing technologies. A cooperative InnoEnergy—EIT financed KIC Knowledge and Innovation Community—research project pursues development and demonstration of highly efficient technologies to overcome the constraints and to yield renewable phosphate fertilizers and energy from waste flows that may have a combined technical energy potential of 3,600 PJ/year and an annual phosphate recovery potential of 4.5–5.5 million tonnes (as P2O5) in Europe. 相似文献
120.
Dr. Kazuhiko Amakawa Dr. Lili Sun Dr. Chunsheng Guo Dr. Michael Hävecker Pierre Kube Prof. Dr. Israel E. Wachs Soe Lwin Prof. Dr. Anatoly I. Frenkel Dr. Anitha Patlolla Prof. Dr. Klaus Hermann Prof. Dr. Robert Schlögl Dr. Annette Trunschke 《Angewandte Chemie (International ed. in English)》2013,52(51):13553-13557
Highly dispersed molybdenum oxide supported on mesoporous silica SBA‐15 has been prepared by anion exchange resulting in a series of catalysts with changing Mo densities (0.2–2.5 Mo atoms nm?2). X‐ray absorption, UV/Vis, Raman, and IR spectroscopy indicate that doubly anchored tetrahedral dioxo MoO4 units are the major surface species at all loadings. Higher reducibility at loadings close to the monolayer measured by temperature‐programmed reduction and a steep increase in the catalytic activity observed in metathesis of propene and oxidative dehydrogenation of propane at 8 % of Mo loading are attributed to frustration of Mo oxide surface species and lateral interactions. Based on DFT calculations, NEXAFS spectra at the O‐K‐edge at high Mo loadings are explained by distorted MoO4 complexes. Limited availability of anchor silanol groups at high loadings forces the MoO4 groups to form more strained configurations. The occurrence of strain is linked to the increase in reactivity. 相似文献