Synthesis and chemistry of strained ring compounds
| dc.contributor.advisor | Billups, W. Edward | en_US |
| dc.creator | Litosh, Vladislav Alexander | en_US |
| dc.date.accessioned | 2009-06-04T06:59:20Z | en_US |
| dc.date.available | 2009-06-04T06:59:20Z | en_US |
| dc.date.issued | 2002 | en_US |
| dc.description.abstract | The gas phase elimination of trimethylsilyl fluoride from beta-halocyclopropylsilanes using solid n-Bu4N+F or CsF adsorbed on glass helices offers a superior route to highly strained alkenes. This approach has been used to synthesize 1-chloro-3-methylenecyclopropene, 1,4-dichlorospiropentadiene, 1,4-dichlorospiropentene, and oxaspiropentene from the appropriate precursors. In each instance the product could be isolated and characterized by low temperature nuclear magnetic resonance spectroscopy. Geometries were defined computationally. The corresponding Diels-Alder adducts of these species with cyclopentadiene or 1,3-butadiene were also obtained and characterized.* Thermolysis of spiro[2.4]hepta-1,4,6-triene at 60°C yields bicyclo[3.2.0]hepta-1,3,5-triene (Ea = 24.7 kcal/mole) which dimerizes in two different fashions forming cyclobutanes. 1,2-Dimethylspiro[2.4]hepta-1,4,6-triene and 1-propylspiro[2.4]hepta-1,4,6-triene also rearrange at 60°C, but at a faster rate, to yield cyclobutane dimers of the corresponding bicyclo[3.2.0]hepta-1,3,5-trienes.* The reactions of benzocyclopropene and cyclopropa[b]naphthalene with metal carbenes were investigated. The cycloproparenes react with Cl2 (Cy3P)2Ru=CH2 to form unstable 3-ruthenabenzocyclopentenes which decompose to give o-xylylenes. o-Xylylenes produced in this way can be trapped as Diels-Alder adducts by dimethyl acetylenedicarboxylate. In contrast, Cp2Ti=CH2 forms moderately stable 2- and 3-titanabenzocyclopentene complexes.* *Please refer to dissertation for diagrams. | en_US |
| dc.format.extent | 240 p. | en_US |
| dc.format.mimetype | application/pdf | en_US |
| dc.identifier.callno | THESIS CHEM. 2002 LITOSH | en_US |
| dc.identifier.citation | Litosh, Vladislav Alexander. "Synthesis and chemistry of strained ring compounds." (2002) Diss., Rice University. <a href="https://hdl.handle.net/1911/18109">https://hdl.handle.net/1911/18109</a>. | en_US |
| dc.identifier.uri | https://hdl.handle.net/1911/18109 | en_US |
| dc.language.iso | eng | en_US |
| dc.rights | Copyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder. | en_US |
| dc.subject | Inorganic chemistry | en_US |
| dc.subject | Organic chemistry | en_US |
| dc.title | Synthesis and chemistry of strained ring compounds | en_US |
| dc.type | Thesis | en_US |
| dc.type.material | Text | en_US |
| thesis.degree.department | Chemistry | en_US |
| thesis.degree.discipline | Natural Sciences | en_US |
| thesis.degree.grantor | Rice University | en_US |
| thesis.degree.level | Doctoral | en_US |
| thesis.degree.name | Doctor of Philosophy | en_US |
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