Impact of reaction products on the Grignard reaction with silanes and ketones

Grignard reactions with alkoxysilanes or carbonyl compounds produce alkoxymagnesium halides as by-products. Kinetic measurements for reactions of silanes and of a ketone were performed with Grignard reagents, enriched in alkoxymagnesium halides and taken in a great excess.The alkoxide-type reaction products complex tightly with Grignard reagents and enhance in this way their nucleophilicity, thus accelerating the reaction. However, alkoxides branched at α-C atom exert an unfavorable steric hindrance to reaction resulting in a decrease in the reaction rate.     

Synthesis of model long-chain ω-alkenyltrichlorosilanes and triethoxysilanes for the formation of self-assembled monolayers

The synthesis of model long-chain hydrocarbons (C₁₃ and C₁₉) carrying a vinyl group and a trichloro- or a triethoxysilyl group at each end is reported. These compounds are suitable for linkage to a hydroxylated silicon surface and at the other end with vinyl group for further functionalization and multilayer formation.     

Improperly efficient solutions in a class of vector optimization problems

Journal of Global Optimization - Improperly efficient solutions in the sense of Geoffrion in linear fractional vector optimization problems with unbounded constraint sets are studied systematically...     

Prediction of brand stories spreading on social networks

Advances in Data Analysis and Classification - Online social network is a major media for many types of information communication. Although the primary purpose of social networks is to connect...     

Non-linear parabolic problem associated with the penetration of a magnetic field into a substance

We study the following initial and boundary value problem: In section 1, with u₀ in L²(Ω), f continuous such that f(u) + ? non-decreasing for ? positive, we prove the existence of a unique solution on (0,T), for each T > 0. In section 2 it is proved that the unique soluition u belongs to L²(0, T; H ∩ H²) ∩ L^∞(0, T; H) if we assume u₀ in H and f in C¹(?,?). Numerical results are given for these two cases.     

Kinetics of the grignard reaction with silanes in diethyl ether and ether-toluene mixtures

Kinetics of the reactions of butylmagnesium chloride and phenylmagnesium bromide with tetraethoxysilane and methyltrichlorosilane was investigated in diethyl ether and diethyl ether-toluene mixtures. Replacement of ether by toluene significantly accelerates the reaction with alkoxysilanes, while no effect was found for the reaction with chlorosilanes. We established that the reaction with alkoxysilanes consists of replacement of a donor molecule at the magnesium center by the silane followed by subsequent rearrangement of the complex to products through a four-center transition state. Chlorosilanes react differently without solvent molecule replacement but also via a four-center transition state. Large negative activation entropies are consistent with formation of cyclic transition states. Small activation enthalpy values together with remarkable exothermicity point to early transition states of the reactions.     

Regioselective synthesis of the bridged tricyclic core of Garcinia natural products via intramolecular aryl acrylate cycloadditions

[reaction: see text] Two different routes to the tricyclic core of Garcinia-derived natural products are described. The first approach is based on a tandem Claisen/Diels-Alder rearrangement and delivers the desired lactone 14. The second approach, employing a Wessely oxidation/Diels-Alder protocol, leads to the same caged heterocycle, albeit with modified constitution.     

Evaluation of a retention model in comprehensive two-dimensional gas chromatography

Modeling the retention in comprehensive two-dimensional gas chromatography (GC x GC) was achieved using retention indices obtained in conventional GC. Predicted results were compared with experimental data obtained in the two-dimensional separation of a synthetic hydrocarbon mixture. This proved to be helpful in optimizing the operating conditions of GC x GC separation of a complex petroleum sample and in identifying chemical families.