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H-bond Donor (h-bond + donor)
Selected AbstractsPolymer-Supported Highly Enantioselective Catalyst for Nitro-Michael Addition: Tuning through Variation of the Number of H-Bond Donors and Spacer LengthADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009Lital Tuchman-Shukron Abstract Two series of polymer-bound bifunctional organocatalysts, based on chiral diamine scaffolds, were prepared by solid-phase synthesis. The series, incorporating a single hydrogen bond donor carbamate functionality, was notably more enantioselective in the Michael reaction of acetone and nitrostyrene than the series that includes a double hydrogen bond donor urea moiety, or the polymer-bound diamine that lacks sufficiently acidic protons. The best aminocarbamate catalyst promoted the addition of acetone to nitroolefins with enantioselectivity unmatched by known heterogeneous catalysts. Introduction of a short linear spacer between the support and the scaffold improves the activity but reduces the selectivity of the catalyst. Alternatively, an increase in the reaction yield could be induced by the benzoic acid additive. [source] A Theoretical Study of Correlation between Hydrogen-Bond Stability and J -Coupling through a Hydrogen BondHELVETICA CHIMICA ACTA, Issue 10 2003Shun-ichi Kawahara trans -Hydrogen-bond hyperfine splitting via magnetic interaction, which is observed as J -coupling in NMR experiments, was theoretically studied. trans -Hydrogen-bond hyperfine splitting should be closely related to the orbital interaction between the lone-pair orbital of the H-bond acceptor and the antibond orbital of the H-bond donor. A linear relationship was observed between magnetic interaction hyperfine splitting through a H-bond and the H-bond strength. The relationship was dependent on the type of the nucleus forming the H-bond; linear correlation was observed in NH,,,O/N type or OH,,,N type H-bonded complexes, but not in OH,,,O type H-bonded complexes. [source] Synthesis and Characterization of Highly Dispersed Antimony-Doped Stannic Hydroxide Nanoparticles: Effects of the Azeotropic Solvents to Remove Water on the Properties and Microstructures of the NanoparticlesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 4 2007Fen Yang Highly dispersed antimony (Sb)-doped stannic hydroxide nanoparticles have been successfully prepared using the solution chemistry method. The properties and microstructures of the nanoparticles are investigated in detail by means of infrared, transmission electron microscope, X-ray diffractometer, and Brunauer-Emmett-Teller nitrogen surface area measurements. The results indicate that the properties and microstructures of the nanoparticles strongly depend on the azeotropic solvents used to remove water at the drying stage. Various azeotropic solvents are screened to investigate their effects on the size and dispersivity of dried Sb-doped stannic hydroxide. Three empirical rules are drawn for selecting an effective azeotropic solvent: (1) the solvent molecule should contain at least one atom such as oxygen as the hydrogen (H)-bond acceptor to form H bonds with the surface ,OH (acting as an H-bond donor) of polymer particle; (2) the H-bond acceptor should locate in the middle of the alkane chain rather than on the terminal so that the alkane chain can stretch out and cover more surface area, improving the dispersivity of the dried product; and (3) the solvent should have a higher boiling point (,140°C) to reduce the time of azeotropic distillation for removing water and maintain a lower residual amount of azeotropic agent. Based on the empirical rules, it is discovered that iso-amyl acetate is the most effective azeotropic solvent. [source] Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas PhaseCHEMPHYSCHEM, Issue 6 2005C. Lomenech Dr. Abstract The adsorption of neutral glycine onto amorphous silica was investigated both theoretically and experimentally. DFT calculations were performed at the BLYP-631++G** level using a cluster approach. Several possible configurations involving the formation of H bonds between glycine and one, two, or three silanol groups (SiOH) were considered. The most favorable bonding of glycine with one silanol group (45 kJ,mol,1) occurs through the COOH moiety, thus forming a cycle in which the CO group is an H-bond acceptor whereas the acidic OH group is an H-bond donor. With two or three silanol groups, additional H bonds are formed between the amine moiety and the silanol groups, which leads to an increased adsorption energy (70 and 80 kJ,mol,1for two and three silanol groups, respectively). Calculated ,CO, ,HNH, and ,HCHvalues are sensitive to the adsorption mode. A bathochromic shift of ,COas compared to the ,COof free glycine (calculated in the 1755,1790 cm,1range) is found for glycine in interaction with silanol(s). The more H bonds are formed between the COOH moiety and silanol groups, the higher the bathochromic shift. For ,HNH, no shift is found for glycine adsorbed on one and two silanol groups (where the amine is either not bound or an H-bond donor), whereas a bathochromic shift is calculated with three silanols when the amine moiety is an H-bond acceptor. Experimental FTIR spectra performed at room temperature for glycine adsorbed at 160,°C on Aerosil amorphous silica exhibit bands at 1371, 1423, 1630, and 1699 cm,1. The experimental/calculated frequencies have their best correspondence for glycine adsorbed on two silanol groups. It is important to note that the forms giving the best correspondence to experimental frequencies are the most stable ones. [source] | ||||||||||