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Development of Viable Synthetic Approaches to Highly Functionalized Small Ring Systems - Synthesis of Novel Cyclopropylacrylates as Monomers for Low-Shrinkage Polymer-Composites

dc.contributor.advisorMeijere, Armin de Prof. Dr.de
dc.contributor.authorBahutski, Viktarde
dc.date.accessioned2005-07-13T15:09:48Zde
dc.date.accessioned2013-01-18T10:38:57Zde
dc.date.available2013-01-30T23:51:05Zde
dc.date.issued2005-07-13de
dc.identifier.urihttp://hdl.handle.net/11858/00-1735-0000-0006-B0A8-Ede
dc.identifier.urihttp://dx.doi.org/10.53846/goediss-2185
dc.format.mimetypeapplication/pdfde
dc.language.isoengde
dc.rights.urihttp://webdoc.sub.gwdg.de/diss/copyr_diss.htmlde
dc.titleDevelopment of Viable Synthetic Approaches to Highly Functionalized Small Ring Systems - Synthesis of Novel Cyclopropylacrylates as Monomers for Low-Shrinkage Polymer-Compositesde
dc.typedoctoralThesisde
dc.title.translatedDevelopment of Viable Synthetic Approaches to Highly Functionalized Small Ring Systems - Synthesis of Novel Cyclopropylacrylates as Monomers for Low-Shrinkage Polymer-Compositesde
dc.contributor.refereeLaatsch, Hartmut Prof. Dr.de
dc.date.examination2004-01-21de
dc.subject.dnb540 Chemiede
dc.description.abstractengTwenty-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 werde
dc.subject.topicMathematics and Computer Sciencede
dc.subject.gerhydrolysede
dc.subject.geroxidationde
dc.subject.gercycloadditionde
dc.subject.gercyclopropanierungde
dc.subject.gerWittig reaktionde
dc.subject.gerenin cycloisomerisierungde
dc.subject.gerpalladiumde
dc.subject.gerkatalysede
dc.subject.gerring-öffnung polymerisationde
dc.subject.gervinylcyclopropanede
dc.subject.enghydrolysisde
dc.subject.engoxidationsde
dc.subject.engcycloadditionsde
dc.subject.engcyclopropanationde
dc.subject.engWittig reactionde
dc.subject.engenyne cyclisomerizationde
dc.subject.engpalladiumde
dc.subject.engcatalysisde
dc.subject.engring-opening polymerizationde
dc.subject.engvinylcyclopropanesde
dc.subject.bk35.52de
dc.identifier.urnurn:nbn:de:gbv:7-webdoc-36-8de
dc.identifier.purlwebdoc-36de
dc.affiliation.instituteFakultät für Chemiede
dc.subject.gokfullSUD 250: Oxydations- und Reduktionsreaktionen {Organische Chemie}de
dc.subject.gokfull400de
dc.subject.gokfull500de
dc.subject.gokfull600de
dc.subject.gokfull650de
dc.subject.gokfullSUE 000: Katalyse in der organischen Chemiede
dc.identifier.ppn497785528de


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