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1.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
2.
Corina Andronescu Justus Masa Richard D. Tilley John J. Gooding Wolfgang Schuhmann 《Current Opinion in Electrochemistry》2021
The complex interplay of restricted mass transport leading to local accumulation or depletion of educts, intermediates, products, counterions and co-ions influences the reactions at the active sites of electrocatalysts when electrodes are rough, three-dimensionally mesoporous or nanoporous. This influence is important with regard to activity, and even more to selectivity, of electrocatalytic reactions. The underlying principles are discussed based on the growing awareness of these considerations over recent years. 相似文献
3.
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
4.
We report on the first observation and studies of a weak delocalizing logarithmic temperature dependence of the conductivity,
which causes the conductivity of the 2D metal to increase as T decreases down to 16 mK. The prefactor of the logarithmic dependence is found to decrease gradually with density, to vanish
at a critical density n
c
, 2∼2×1012 cm−2, and then to have the opposite sign at n>n
c
,2. The second critical density sets the upper limit on the existence region of the 2D metal, whereas the conductivity at the
critical point, G
c
,2∼120e
2/h, sets an upper (low-temperature) limit on its conductivity.
Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 497–501 (25 September 1998)
Published in English in the original Russian journal. Edited by Steve Torstveit. 相似文献
5.
Wolfgang Kliesch 《Mathematische Nachrichten》1989,142(1):181-213
The paper gives an approach to the topological degree in Rn which takes into account numerical requirements and permits derivation of the known degree computation formulas in a simple way. The new approach subsumes several earlier approaches and represents a general principle of construction of degree computation formulas. The basic idea consists of computing the degree of a continuous function relative to a bounded open subset Ω of Rn by means of an auxiliary function which is defined on a polyhedron approximating Ω and maps into a known fixed convex polyhedron containing the origin of Rn. It is further shown that the topological degree of a continuous function relative to an n-dimensional polyhedron P can be computed alone by means of a subset of the boundary of P . 相似文献
6.
Nuclear Magnetic Resonance (NMR) was used to investigate the extrusion behaviour of PTFE pastes in a ram extruder. By means
of 1H-NMR imaging (MRI) it is possible to determine the local proton density and therefore, the local fluid concentration. The
19F-MRI provides the local solid concentration. Thus the local saturation and the local porosity can be calculated with the
information of the local fluid and solid concentration. Furthermore displacement profiles can be derived from NMR images by
means of correlation techniques without any preparation or marking of the pastes.
Received: 8 May 2000 Accepted: 1 May 2001 相似文献
7.
8.
D. De Salvador A. Coati E. Napolitani M. Berti A.V. Drigo M.S. Carroll J.C. Sturm J. Stangl G. Bauer L. Lazzarini 《Applied Physics A: Materials Science & Processing》2002,75(6):667-672
In this work we investigate the diffusion and precipitation of supersaturated substitutional carbon in 200-nm-thick SiGeC
layers buried under a silicon cap layer of 40 nm. The samples were annealed in either inert (N2) or oxidizing (O2) ambient at 850 °C for times ranging from 2 to 10 h. The silicon self-interstitial (I) flux coming from the surface under
oxidation enhances the C diffusion with respect to the N2-annealed samples. In the early stages of the oxidation process, the loss of C from the SiGeC layer by diffusion across the
layer/cap interface dominates. This phenomenon saturates after an initial period (2–4 h), which depends on the C concentration.
This saturation is due to the formation and growth of C-containing precipitates that are promoted by the I injection and act
as a sink for mobile C atoms. The influence of carbon concentration on the competition between precipitation and diffusion
is discussed.
Received: 19 October 2001 / Accepted: 19 December 2001 / Published online: 20 March 2002 / Published online: 20 March 2002 相似文献
9.
Many problems arising in practical applications lead to linear programming problems. Hence, they are fundamentally tractable. Recent interior-point methods can exploit problem structure to solve such problems very efficiently. Infeasible interior-point predictor–corrector methods using floating-point arithmetic sometimes compute an approximate solution with duality gap less than a given tolerance even when the problem may not have a solution. We present an efficient verification method for solving linear programming problems which computes a guaranteed enclosure of the optimal solution and which verifies the existence of the solution within the computed interval. 相似文献