Synthesis and Properties of TRANSDIP,a Rigid Chelator Built upon a Cyclodextrin Cavity: Is TRANSDIP an Authentic trans‐Spanning Ligand?

The C2-symmetrical diphosphane TRANSDIP was obtained in high yield by treating 6A,6B,6D,6E-tetramesylated, permethylated alpha-cyclodextrin with PPhLi2 in excess. The double cascade cyclisation thus produced is regioselective as phosphinidene capping involves only adjacent glucose units. It is also stereospecific, as both lone pairs on the phosphorus atoms are orientated towards the cyclodextrin axis. The restricted flexibility of the phosphorus atoms, which are part of nine-membered heterocyclic rings, is responsible for JP,C spin-spin couplings with the eight-bond distant CH2OMe carbon atoms of glucose units C and F. The treatment of TRANSDIP with Group 10 metal dihalides quantitatively gave square-planar chelate complexes, in which a M--X bond points towards the centre of the cavitand. The favourable P...P separation and the directional control of the lone pairs on the phosphorus atoms rule out the possibility of forming binuclear complexes or higher oligomers. Further, in all the complexes, the phosphorus atoms are in a trans arrangement. TRANSDIP may therefore be regarded as an authentic trans-spanning diphosphane. In the complex [NiBr2TRANSDIP], the cavity provides effective protection of the encapsulated M--X bond towards nucleophilic attack by MeLi. The same complex, upon activation with methylaluminoxane, efficiently dimerises ethene and propene.     

Oxidation reactivity channels for 2-(pyridin-2-yl)-N,N-diphenylacetamides

Synthetic routes to 2-(pyridin-2-yl)-N,N-diphenylacetamide and 2-(6-methylpyridin-2-yl)-N,N-diphenyl-acetamide are described along with results from the chemical oxidation of these compounds with peracetic acid, m-chloroperbenzoic acid, and OXONE. In each case, oxidations generate four products in varying amounts depending on the oxidant and reaction conditions. Each product has been characterized by spectroscopic methods and the molecular structures of several of the new compounds have been confirmed by X-ray crystallography.     

Microstructure and physico-chemical transformation of some common woods from Cameroon during drying

Journal of Thermal Analysis and Calorimetry - The influence of drying on the microstructure, physical and chemical properties of some tropical wood species has been investigated using...     

Alkynylcyclohexadienyl tricarbonyliron complexes: A new directing effect for organoiron-mediated synthesis

The first example of an alkyne-substituted tricarbonyl(η⁵-cyclohexadienyl)iron(1+) complex has been prepared and the ω directing effect of the phenylethynyl substituent has been demonstrated in nucleophile addition reactions. Addition of NC⁻ also occurs at the a position to form an unusual η¹, η³-structure.     

Finite volume schemes for nonhomogeneous scalar conservation laws: error estimate

Summary. In this paper, we study finite volume schemes for the nonhomogeneous scalar conservation law with initial condition . The source term may be either stiff or nonstiff. In both cases, we prove error estimates between the approximate solution given by a finite volume scheme (the scheme is totally explicit in the nonstiff case, semi-implicit in the stiff case) and the entropy solution. The order of these estimates is in space-time -norm (h denotes the size of the mesh). Furthermore, the error estimate does not depend on the stiffness of the source term in the stiff case. Received October 21, 1999 / Published online February 5, 2001     

Formal Verification of Numerical Programs: From C Annotated Programs to Mechanical Proofs

Numerical programs may require a high level of guarantee. This can be achieved by applying formal methods, such as machine-checked proofs. But these tools handle mathematical theorems while we are interested in C code, in which numerical computations are performed using floating-point arithmetic, whereas proof tools typically handle exact real arithmetic. To achieve this high level of confidence on C programs, we use a chain of tools: Frama-C, its Jessie plugin, Why and provers among Coq, Gappa, Alt-Ergo, CVC3 and Z3. This approach requires the C program to be annotated: each function must be precisely specified, and we prove the correctness of the program by proving both that it meets its specifications and that no runtime error may occur. The purpose of this paper is to illustrate, on various examples, the features of this approach.     

Vibrational spectroscopic investigation of the phase diagram of a biomimetic lipid monolayer

The phase behavior of a biomimetic monolayer consisting of diphospholipid molecules on water is investigated using vibrational sum-frequency generation and fluorescence microscopy. In addition to the transition from the-molecularly disordered-liquid phase to the highly ordered and oriented con-densed phase, a novel, extremely sharp transition is observed at low compression, which is attributed to the uncurling of the hydrophobic alkane chains upon compression.