Addition of a stoichiometric amount of HCl to alkenylaldimines, -formamidines, and -amidines results in the protonation of the sp2-nitrogen atom. The resulting alkenylaldiminium, -formamidinium, and -amidinium salts can be isolated and fully characterized, including single-crystal X-ray diffraction studies. Heating solutions of these salts induces ring closure cleanly and regioselectively via formal "exo" addition of the nitrogen-hydrogen bond to the pendent carbon-carbon double bond, affording the corresponding cyclic aldiminium, dihydroisoquinolinium, and imidazolinium salts. Of special interest, novel 4,4-disubstituted imidazolinium salts are accessible via this synthetic route. Similarly, addition of phosgene to alkenyl ureas and alkenyl amides, followed by gentle heating, cleanly affords C-chloro imidazolinium, and cyclic C-chloro iminium salts, respectively. Treatment of the latter with tetrakis(triphenylphosphine)palladium allows for the preparation of the first transition-metal complex bearing a cyclic arylaminocarbene as ligand. Deuterium labeling experiments suggest that the mechanism of the hydroiminiumation and -amidiniumation reactions involves an intramolecular proton transfer to the double bond in the rate-determining step. This novel synthetic methodology gives access to a variety of N-heterocyclic carbene (NHC) and cyclic alkyl- and arylaminocarbene (CAAC) precursors. 相似文献
Structural Chemistry - Malaria is an important disease causing many death in several countries of Africa and Asia. In these continents, some plants such as Garcinia cola are used to fight against... 相似文献
Welding processes involve high temperatures and metallurgical and mechanical consequences that must be controlled. For this purpose, numerical simulations have been developed to study the effects of the process on the final structure. During the welding process, the material undergoes thermal cycles that can generate different physical phenomena, like phase changes, microstructure changes and residual stresses and distortions. But the accurate simulation of transient temperature distributions in the part needs to carefully take account of the fluid flow in the weld pool. The aim of this paper is thus to propose a new approach for such a simulation taking account of surface tension effects (including both the “curvature effect” and the “Marangoni effect”), buoyancy forces and free surface motion.The proposed approach is validated by two numerical tests from the literature: a sloshing test and a plate subjected to a static heat source. Then, the effects of the fluid flow on temperature distributions are discussed in a hybrid laser/arc welding example. 相似文献
ZDM – Mathematics Education - This paper aims at contributing to remedy the narrow treatment of functions at upper secondary level. Assuming that students make sense of functions by working... 相似文献
A range of new diimidazolium salts, held together by an alkyl unit and bearing alcohol pendant arms on their nitrogen, was synthesized. A short modular reaction pathway leads to the N-heterocyclic carbene (NHC) precursors, differing by the flexibility of the bridge, the steric bulk of substituents in α-position of the OH groups and the anions. Treatment of diimidazolium salts with Ag2O yields AgI(carbene)2 complexes. The related trimethylene-bridged bis-NHC silver complexes 6 and 7 were crystallised with di-tosylate and di-hexafluorophosphate anions, respectively. Their X-ray structures revealed dimeric species, involving two ligands with different arrangements around the Ag cations, leading to crossed and parallel conformations. 相似文献
On the basis of linear hydrodynamics, we analyze the trajectory of particle-hedgehog systems, attracted by a -1/2 disclination (defect line) in a nematic liquid crystal. We show that, as with the interactions between like-particles, the interaction between a particle and a disclination has an electrostatic analogue, the splay replacing the electric field, except for the symmetry properties. The disclination thus attracts the beads along nonradial tracks and in a self-assembling process, or template mechanism, may build a microscopic necklace with them. 相似文献
Indium tin oxide (ITO) is the most commonly used transparent conducting substance. It has been used in numerous applications such as light-emitting diodes. In most applications and studies, the ITO surface is further coated with additional layers. The interface between the ITO and the coating is of utmost importance since it affects the physical and chemical properties of the final device. Improving the adhesion between ITO and a coating layer can be achieved by applying a “molecular adhesive” as an inter-phasing molecular layer. In this study, we used 3-(trimethoxysilyl)propyl methacrylate as a “molecule adhesive” for better connection between ITO and a polymethacrylate layer. The samples were studied by electrochemistry, contact angle goniometry, atomic force microscopy, and nano scratch microscopy. These studies clearly show that a simple silanization process formed a thin molecular adhesive layer, which did not influence the physical and chemical properties of the final coated electrode and at the same time increased significantly the adhesion between the ITO and the polymethacrylate coating.
We consider the problem of minimizing an indefinite quadratic form over the nonnegative orthant, or equivalently, the problem of deciding whether a symmetric matrix is copositive. We formulate the problem as a difference of convex functions problem. Using conjugate duality, we show that there is a one-to-one correspondence between their respective critical points and minima. We then apply a subgradient algorithm to approximate those critical points and obtain an efficient heuristic to verify non-copositivity of a matrix. 相似文献