Search results for "norbornen"
showing 10 items of 40 documents
New practical tungsten(VI) based catalyst systems for ring opening metathesis polymerisation
2002
Abstract Tungsten(VI) complexes of the type trans -[WCl 2 (diol)(OAr) 2 ] were studied as catalyst precursors for ROMP of norbornene and dicyclopentadiene. These compounds form active catalysts when treated by simple Grignard reagents, such as methyl magnesium iodide or neophyl magnesium chloride. Moreover, polymerisations can be run under ambient atmosphere without complicated inert atmosphere techniques.
Nanoporous Thin Films Based on Polylactide-Grafted Norbornene Copolymers
2008
Thermally stable vinyl polymerized polynorbornene (PNB) is one of the challenging materials in porous low dielectric films for packaging applications. Nanoporous PNB thin films were obtained with poly(d,l-lactide) (PLA)-grafted norbornene copolymers. Thermally labile PLA chains act as pore generators in PNB films. Thermally stable PNB main chains were synthesized by Pd-catalyzed vinyl polymerization and PLA side chains were grafted onto the PNB main chains by ring opening polymerization. The brittle and poor processible properties of PNB could easily be controlled by the copolymerization with norbornene derivatives. In thin films, the PLA chains were found to thermally decompose at about 25…
An All-ROMP Route to Graft Copolymers
2007
A new versatile synthesis strategy for macromonomers has been developed that uses the living ring-opening metathesis polymerization (ROMP) with commercial Grubbs first generation ruthenium initiators. Homopolymers as well as diblock copolymers were end-functionalized with norbornene derivatives to serve as macromonomers. The graft copolymerization of the macromonomers was also carried out employing ROMP. Well-defined and highly functional graft copolymers are accessible by this new synthetic route.
Synthesis of Pyrrolo[1,2-a]pyrimidine Enantiomers via Domino Ring-Closure followed by Retro Diels-Alder Protocol
2017
From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2-a]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA) protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid. peerReviewed
Tungsten(VI) complexes with aminobis(phenolato) [O,N,O] donor ligands.
2004
The reaction between trisdiolatotungsten(VI) complex [W(eg)(3)] (1) (eg = 1,2-ethanediolato dianion) and phenolic ligand precursor methylamino-N,N-bis(2-methylene-4,6-dimethylphenol) (H(2)L(Me)) or methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol) (H(2)L(tBu)) affords monomeric oxotungsten complex [WO(eg)(L(Me))] (2) or [WO(eg)(L(tBu))] (3), respectively. These complexes react further with chlorinating reagents, which leads to the displacement of ethanediolato ligands from the complex units and formation of cis and trans isomers of the corresponding dichloro complexes [WOCl(2)(L(Me))] (4) and [WOCl(2)(L(tBu))] (5), respectively. Identical dichloro complexes were also prepared by …
Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts
2020
The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discusse…
Synthesis of Functional Block Copolymers Carrying One Poly(p-phenylenevinylene) and One Nonconjugated Block in a Facile One-Pot Procedure
2016
Block copolymers composed of a MEH–PPV block and a nonconjugated functional block (molecular weights between 5 and 90 kg/mol) were synthesized in a facile one-pot procedure via ROMP. This one-pot procedure permits the synthesis of numerous block copolymers with little effort. Amphiphilic block copolymers were obtained via incorporation of oxanorbornene carrying a PEG side chain as well as via postpolymerization modification of a reactive ester carrying norbornene derivative with methoxypoly(ethylene glycol)amine. These amphiphilic block copolymers can be self-assembled into micelles exhibiting different sizes (60–95 nm), morphologies (micelles or fused, caterpillar-like micelles), and optic…
Vanadium catalysts for ethylene-norbornene copolymerization
2020
Cyclic olefin copolymers (COCs) are a promising group of materials with specific, projectable properties. In this group, copolymers of ethylene and norbornene are of particular interest. A variety of transition metal complexes are used for their synthesis, mostly elements from group 4. This review presents the application of vanadium catalysts with various types of ligands in the synthesis of ethylene-norbornene copolymers. The influence of ligands and reaction conditions on the activity of catalyst and selected properties of copolymers are described in this paper.
Chiral diphosphine derivatives of alkylidyne tricobalt carbonyl clusters – A comparative study of different cobalt carbonyl (pre)catalysts for (asymm…
2016
Reaction of the tricobalt carbyne cluster [Co-3(mu(3)-CH)(CO)(9)] with chiral diphosphines of the Josiphos and Walphos families affords the new clusters [Co-3(mu(3)-CH)(CO)(7)(P-P*)] in good yield (P-P* = J004 (1), J005 (2), J007 (3), W001 (4), W003 (5)). The new alkylidyne tricobalt clusters, and the previously known [Co-3(mu(3)-CH)(CO)(7)(mu-J003)], have been tested as catalysts/catalyst precursors for intermolecular Pauson-Khand cyclization, using norbornene and phenylacetylene as substrate. The diphosphine-substituted tricobalt carbonyl clusters proved to be viable catalysts/catalyst precursors that gave products in moderate to good yields, but the enantiomeric excesses were low. When t…
Isomerization and Application of Aroylnorbornenecarboxylic Acids for Stereoselective Preparation of Heterocycles
2002
When boiled in acidic or basic solution, diendo-3-aroylbicyclo[2.2.1]heptane-2-carboxylic acids (1 and la) isomerize to exo-3-aroylbicyclo[2.2.1]heptane-endo-2-carboxylic acids (2 and 2a). Similar endo→exo and even exo → endo isomerization of the aroyl group occurred when the Diels-Alder product containing a mixture of 3-exo-p-toluoylbicyclo[2.2.1 ]hept-5-ene-2-endo-carboxylic acid (4) and 3-endo-p-toluoylbicyclo[2.2.1]hept-5-ene-2-exo-carboxylic acid (5) was reacted with bifunctional reagents: o-aminothiophenol, 3-amino-1-propanol, 1,4-diaminobutane or diexo-3-hydroxymethylbicyclo[2.2.1]heptane-2-amine. All the reactions yielded mixtures of norbornene diendo- and diexo-fused heterocycles (…