Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

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.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

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.     

A Unified Constructive Approach to the Topological Degree in Rn

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 .     

Extrusion of pastes with a piston extruder for the determination of the local solid and fluid concentration, the local porosity and saturation and displacement profiles by means of NMR imaging

 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     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

The canonical solution operator of $ {\bar \partial } $ on weighted spaces with holomorphic coefficients

On weighted spaces with strictly plurisubharmonic weightfunctions the canonical solution operator of and the ‐Neumann operator are bounded. In this paper we find a class of strictly plurisubharmonic weightfunctions with certain growth conditions, so that they are Hilbert‐Schmidt operators between weighted spaces with different weightfunctions, if they are restricted to forms with holomorphic coefficients. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An Addendum to Birkhoff's Theorem

In spherically symmetric systems, in spite of Birkhoff's Theorem, the rates of clocks in vacuum regions on either side of moving mass shells must be continually readjusted to stay in synchrony. This shows up as time-dependence of the metric in terms of the globally meaningful time coordinate.