dc.contributor.advisor | Meijere, Armin de Prof. Dr. | de |
dc.contributor.author | Bahutski, Viktar | de |
dc.date.accessioned | 2005-07-13T15:09:48Z | de |
dc.date.accessioned | 2013-01-18T10:38:57Z | de |
dc.date.available | 2013-01-30T23:51:05Z | de |
dc.date.issued | 2005-07-13 | de |
dc.identifier.uri | http://hdl.handle.net/11858/00-1735-0000-0006-B0A8-E | de |
dc.identifier.uri | http://dx.doi.org/10.53846/goediss-2185 | |
dc.format.mimetype | application/pdf | de |
dc.language.iso | eng | de |
dc.rights.uri | http://webdoc.sub.gwdg.de/diss/copyr_diss.html | de |
dc.title | Development of Viable Synthetic Approaches to Highly Functionalized Small Ring Systems - Synthesis of Novel Cyclopropylacrylates as Monomers for Low-Shrinkage Polymer-Composites | de |
dc.type | doctoralThesis | de |
dc.title.translated | Development of Viable Synthetic Approaches to Highly Functionalized Small Ring Systems - Synthesis of Novel Cyclopropylacrylates as Monomers for Low-Shrinkage Polymer-Composites | de |
dc.contributor.referee | Laatsch, Hartmut Prof. Dr. | de |
dc.date.examination | 2004-01-21 | de |
dc.subject.dnb | 540 Chemie | de |
dc.description.abstracteng | Twenty-eight new alkyl 2-cyclopropylacrylates with various substitution patterns were synthesized from readily available precursors applying appropriately modified variants of standard transformations or newly developed synthetic protocols. Towards the synthesis of target cyclopropyl acrylates a preparative-scale procedur vapor-phas yrolysis o bicyclopropylidene to methylenespiropentane to provide pure methylenespiropentane on a 17.4 g scale, a large-scal reparative protocol fo 2-methylenecyclopropanecarboxaldehyde, two highly efficien for hydrolysis of alkyl acrylates and partia ers, and new esterification protocol for acylation o sterically congested alcohols were developed. Subsequent cyanohydrin formation from an aldehyde, alcoholysis of a cyanohydrin to an a-hydroxycarboxylic acid ester, Simmons-Smith cyclopropanations of cycloalken-1-yl hydroxyacetates, oxidatio ig methylenation of an a-ketocarboxylic acid ester afforded target cyclopropylacrylates on overall yields ranged from 33 to 54% 0]alken-(n+3)-yl)pyruvates were prepared by dirhodiu tetraacetate-catalyzed cyclopropanation of the corresponding alkenes wit methy 32 58 opropanations of EWG-substituted a-cyclopenteylacetic esters or their isomeric precursors with SHI carbenoid (CF3COOZnCH2I) were investigated. Thus, a protocol fo one-pot cyclopropanation-methylenation of (cyclo)alkylidenemalonates and their analogues, readily accessible by the KNOEVENAGEL reaction, has been developed.The behavior of the synthesized cyclopropylacrylates unde merization condition been investigate (IVOCLAR Vivadent) t demonstrate for alkyl acrylates bearing in a-position 2- o mprove ty in comparison to DECVCP. It was concluded that suc could b bstitut mmerciall lable dilutents i dental composites. Thus le protoco as developed which allow one to obtain methyl 2-(bicyclo[3.1.0]hex-1-yl)acrylate (130) in three steps from hydroxyacetate 81 on a 50 scal in 75 overall yield tive protocol fo 5-exo-trig/3-exo-trig cascade cyclization of various 1,6-enyne been developed which involved a new catalyti haracterized by the lowest loading volume among the published ones. By this approach, the bicyclic 2-cyclopropylacrylate 130 as well as its structural analogues 207-209, which are promising new low-shrinkage monomers an are inaccessibl by other synthetic routes, can be synthesized in high yield.Twenty-eight new alkyl 2-cyclopropylacrylates with variou ns wer | de |
dc.subject.topic | Mathematics and Computer Science | de |
dc.subject.ger | hydrolyse | de |
dc.subject.ger | oxidation | de |
dc.subject.ger | cycloaddition | de |
dc.subject.ger | cyclopropanierung | de |
dc.subject.ger | Wittig reaktion | de |
dc.subject.ger | enin cycloisomerisierung | de |
dc.subject.ger | palladium | de |
dc.subject.ger | katalyse | de |
dc.subject.ger | ring-öffnung polymerisation | de |
dc.subject.ger | vinylcyclopropane | de |
dc.subject.eng | hydrolysis | de |
dc.subject.eng | oxidations | de |
dc.subject.eng | cycloadditions | de |
dc.subject.eng | cyclopropanation | de |
dc.subject.eng | Wittig reaction | de |
dc.subject.eng | enyne cyclisomerization | de |
dc.subject.eng | palladium | de |
dc.subject.eng | catalysis | de |
dc.subject.eng | ring-opening polymerization | de |
dc.subject.eng | vinylcyclopropanes | de |
dc.subject.bk | 35.52 | de |
dc.identifier.urn | urn:nbn:de:gbv:7-webdoc-36-8 | de |
dc.identifier.purl | webdoc-36 | de |
dc.affiliation.institute | Fakultät für Chemie | de |
dc.subject.gokfull | SUD 250: Oxydations- und Reduktionsreaktionen {Organische Chemie} | de |
dc.subject.gokfull | 400 | de |
dc.subject.gokfull | 500 | de |
dc.subject.gokfull | 600 | de |
dc.subject.gokfull | 650 | de |
dc.subject.gokfull | SUE 000: Katalyse in der organischen Chemie | de |
dc.identifier.ppn | 497785528 | de |