Co-melting of solid sucrose and multivalent cation soaps for solvent-free synthesis of sucrose esters

Sucrose fatty acid esters, useful as mild surfactants, have been synthesised in good yields in a solvent-free medium. High contents of monoesters and low saponification rate have been observed. The co-melting of sucrose and a multivalent cation soap such as magnesium or zinc soaps, under basic conditions, allowed the formation of a homogeneous reaction mixture, where solid sucrose was fully dissolved. The kinetic monitoring profiles are similar to reactions in homogeneous solutions, with fast initial formation of monoesters. As a consequence, conversion of sucrose in sucrose esters occurred in good yields. The specificity of multivalent cation soaps compared to monovalent cation soaps, for example, potassium stearate, was pointed out.     

2,2'-Biphosphinines and 2,2'-bipyridines in homoleptic dianionic Group 4 complexes and neutral 2,2'-biphosphinine Group 6 d(6) metal complexes: octahedral versus trigonal-prismatic geometries

The geometric and electronic structure of formally d(6) tris-biphosphinine [M(bp)(3)](q) and tris-bipyridine [M(bpy)(3)](q) complexes were studied by means of DFT calculations with the B3LYP functional. In agreement with the available experimental data, Group 4 dianionic [M(bp)(3)](2-) complexes (1P-3P for M=Ti, Zr, and Hf, respectively) adopt a trigonal-prismatic (TP) structure, whereas the geometry of their nitrogen analogues [M(bpy)(3)](2-) (1N-3N) is nearly octahedral (OC), although a secondary minimum was found for the TP structures (1N'-3N'). The electronic factors at work in these systems are discussed by means of an MO analysis of the minima, MO correlation diagrams, and thermodynamic cycles connecting the octahedral and trigonal-prismatic limits. In all these complexes, pronounced electron transfer from the metal center to the lowest lying pi* ligand orbitals makes the d(6) electron count purely formal. However, it is shown that the bp and bpy ligands accommodate the release of electron density from the metal in different ways because of a change in the localization of the HOMO, which is a mainly metal-centered orbital in bp complexes and a pure pi* ligand orbital in bpy complexes. The energetic evolution of the HOMO allows a simple rationalization of the progressive change from the TP to the OC structure on successive oxidation of the [Zr(bp)(3)](2-) complex, a trend in agreement with the experimental structure of the monoanionic complex. The geometry of Group 6 neutral complexes [M(bp)(3)] (4P and 5P for M=Mo and W, respectively) is found to be intermediate between the TP and OC limits, as previously shown experimentally for the tungsten complex. The electron transfer from the metal center to the lowest lying pi* ligand orbitals is found to be significantly smaller than for the Group 4 dianionic analogues. The geometrical change between [Zr(bp)(3)](2-) and [W(bp)(3)] is analyzed by means of a thermodynamic cycle and it is shown that a larger ligand-ligand repulsion plays an important role in favoring the distortion of the tungsten complex away from the TP structure.     

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

The crystallisation behaviour of (RS)‐diprophylline (DPL) in two different solvents is investigated to assess the incidence of solvated pre‐associations on nucleation, crystal growth and chiral discrimination. In the solvated state, Raman spectroscopy shows that dimeric associations similar to those depicted in the crystalline solid solution (ssRII) predominate in isopropanol (IPA), which may account for the systematic spontaneous nucleation of this crystal form from this solvent. By contrast, spontaneous nucleation in DMF yields the stable racemic compound RI, consistently with the distinct features of the Raman spectrum collected in this solvent. A crystal growth study of ssRII in IPA reveals that the crystal habitus is impacted by the solution enantiomeric excess; this is explained by increased competition between homo‐ and heterochiral pre‐associations. This is supported by a molecular modelling study on the enantiomeric selectivity of the DPL crystal lattices. The combination of assessment methods on solution chemistry, nucleation and chiral discrimination provides methodological tools from which the occurrence of solid solutions can be rationalised.     

Fluorogenic Behaviour of the Hetero‐Diels–Alder Ligation of 5‐Alkoxyoxazoles with Maleimides and their Applications

Fluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero‐Diels–Alder reaction of 5‐alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions.     

Controlled silicon surface functionalization by alkene hydrosilylation

Immobilization of indene ligands onto two types of hydrogen-terminated surfaces, oxide-free Si [H/Si(111)] and oxidized Si [H/SiO2/Si], has been investigated by infrared absorption spectroscopy. The activity of a common catalyst (H2PtCl6) is shown to depend critically on the nature of the solvent. For instance, 2-propanol preferentially reacts with the surface, preventing any ligand attachment. Chlorobenzene is more stable, allowing some ligand attachment, but the H2PtCl6 catalyst also fosters silicon oxidation. In contrast, UV irradiation on oxide-free surfaces promotes a cleaner and more efficient reaction, leading to ligand attachment without substrate oxidation. The complete inactivity of H-terminated surfaces with a thin oxide layer [H/SiO2/Si] suggests that the UV-induced immobilization is mediated solely by the excitation of electron-hole pairs (excitons) in the substrate and is not the result of direct Si-H bond breaking.     

Mécanisme de solvolyse des cis- et trans-(p-toluènesulfonates) d'aryl-2-cyclopentyle I. Etude de la première étape de la solvolyse: effets isotopiques de l' atone de deutérium en position 2, effets de sel basique et effet spécial de sel

Solvolysis Mechanism of cis - and trans-2-Arylcylopentyl p-Toluenesulfonates. The Step: 1-Deuterium Isotope Effects, Basic Salt Effects, and Special Salt Effect We have studied the first step of the solvolysis of cis and trans-2-arylcyclopentyl p-toluenesulfonates in HCOOH, AcOH, and EtOh. All substrates show a high kinetic 1-deuterium isotope effect (k_H/k_D(1) >1.15). This fact indicates that first step leads to classical intimate ion-pair Which dissociates to a solvet-separated ion-pair, without participation either of solvent, the 2-aryl group, or a H-atom at C(2). The slight influence of added basic ions on reaction rate allows us to exclude any direct solvent attack on the covalent substrate even in the most favorable case, i.e. ethanolysis of 2-(p-nitrophenyl)cylopentyl-p-toluenesulfonates. Furthermore, solvent-separated ion pair formation is indicated by the special salt effect induced by LiClO₄.     

Thermotropic liquid crystals from N-alkylpyridinium halides ω-substituted with a mesogenic group

A series of N-alkylpyridinium halides ω-substituted with a 4-methoxybiphen-ylyloxy mesogenic group were synthesized and characterized. The molecules of these compounds contain three distinct parts: a flexible aliphatic chain, a rigid polarizable aromatic core, and a positively charged pyridinium ring associated with a negatively charged counterion. Their thermotropic liquid-crystalline behaviour was studied by differential scanning calorimetry and optical microscopy. Three types of smectic mesophase, namely A, B, and E, were identified by X-ray diffraction. Their structure consists of single layers of upright molecules laterally arranged head to tail. Segregated from the non-ionic parts of the molecules, the ionic end groups are set in double layers with the oppositely charged species facing each other and equally distributed between the two sub-layers. For the ordered smectic E phases, the anions are arranged in rows along the rectangular two dimensional unit cell diagonals with the pyridinium rings sandwiched between them in a chevron-type structure. As for smectic mesophases obtained with soaps, the smectic ordering described in the present work relies primarily on the electrical interactions of the ionic endgroups. Although present, the van der Waals repulsions of the aliphatic and aromatic moieties turn out to be ineffectual.     

Some Remarks on a Vibro-Impact Scheme

We consider a mechanical system subject to a unilateral constraint for which an impact law is defined. The impact process is considered to be instantaneous and the behavior at the impact is described through a restitution coefficient e. We solve this problem using an algorithm developed and used by Paoli and Schatzman. We show that this algorithm develops numerical instabilities related to the restitution coefficient used in the impact law. Finally, we propose a new scheme which introduces some numerical damping in order to avoid the numerical instabilities.     

Applications harmoniques, applications pluriharmoniques et existence de 2-formes parallèles non nulles

In this paper we study harmonic maps from a compact riemannian manifold equiped with a non trivial parallel 2-form, to a K?hler manifold of strongly negative curvature tensor or a riemannian manifold of strictly negative complex sectional curvature. In a first part we set up some rigidity results of Siu type. Then we obtain an upper bound for the rank of such maps in terms of the rank of the 2-form and deduce some vanishing theorems. Received: March 4, 1996