6 resultados para ALKYL-HALIDES
em Archivo Digital para la Docencia y la Investigación - Repositorio Institucional de la Universidad del País Vasco
Resumo:
A family of chiral ligands derived from alpha-phenylethylamine and 2-aminobenzophenone were prepared by alkylation of the nitrogen atom. Upon reaction with glycine and a Ni(II) salt, these ligands were transformed into diastereomeric complexes, as a result of the configurational stability of the stereogenic nitrogen atom. Different diastereomeric ratios were observed depending on the substituent R introduced in the starting ligand, and stereochemical assignments were based on X-ray analysis, along with NMR studies and optical rotation measurements.
Resumo:
"Click" chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the "metal-free" cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing beta-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of beta-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine "click" chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs.
Resumo:
The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid-solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the p-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.
Resumo:
A broad perspective of various factors influencing alkene selenenylation has been developed by concurrent detailed analysis of key experimental and theoretical data, such as asymmetric induction, stereochemistry, relative reactivities, and comparison with that of alkene sulfenylation. Alkyl group branching a to the double bond was shown to have the greatest effect on alkene reactivity and the stereochemical outcome of corresponding addition reactions. This is in sharp contrast with other additions to alkenes, which depend more on the degree of substitution on C=C or upon substituent electronic effects. Electronic and steric effects influencing asymmetric induction, stereochemistry, regiochemistry, and relative reactivities in the addition of PhSeOTf to alkenes are compared and contrasted with those of PhSCl.
Resumo:
256 p.
Resumo:
postprint