Studies on the synthesis and properties of cyclopropenes
| dc.contributor.advisor | Billups, W. Edward | en_US |
| dc.creator | Lee, Gon-Ann | en_US |
| dc.date.accessioned | 2009-06-04T00:43:17Z | en_US |
| dc.date.available | 2009-06-04T00:43:17Z | en_US |
| dc.date.issued | 1990 | en_US |
| dc.description.abstract | Tetra-n-butylammonium fluoride supported on glass helices was used to generate cyclopropenes in the gas phase from $\beta$-halocyclopropylsilanes using the vacuum gas-solid reaction (VGSR) technique. Bicyclo (4.1.0) hept-1,7-ene (1), bicyclo (4.1.0) hept-1,6-ene (2), and bicyclo (5.1.0) oct-1,8-ene (3) were prepared from the appropriate $\beta$-chlorocyclopropylsilanes.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) Compounds 1 and 2 underwent ene reactions to give the same dimer 4. Compound 4 isomerized to 5 via cyclopropene-vinyl carbene rearrangements. Dimerization of 4 led to the cycloaddition adducts 6 and 7 (tetramers of 1).(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) Treatment of either 4 or 5 with oxygen formed 2-(bicyclo (4.1.0) hept-1-yl)-1-cyclohexenecarboxaldehyde (8) and 1-(bicyclo (4.1.0) hept-1-yl)-cyclohepten-3-one (9).(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) Hydrogenation 4 and 5 below $-$20$\sp\circ$C yielded products identified provisionally as 10 and 11, respectively. Both 10 and 11 rearranged to meso-1-(bicyclo (4.1.0) hept-1-yl)bicyclo (4.1.0) heptane (12).(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) Cyclopropene 3 also reacted via an ene reaction to give both dimer and trimer. Tricyclo (5.5.0.0$\sp{1,6}$) decane (13) was prepared by reduction of the butadiene Diels-Alder adduct of 3. Hydrogenation of 3 gave cis-bicyclo (5.1.0) octane and 1-methylcycloheptane.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) | en_US |
| dc.format.extent | 120 p. | en_US |
| dc.format.mimetype | application/pdf | en_US |
| dc.identifier.callno | Thesis Chem. 1990 Lee | en_US |
| dc.identifier.citation | Lee, Gon-Ann. "Studies on the synthesis and properties of cyclopropenes." (1990) Diss., Rice University. <a href="https://hdl.handle.net/1911/16362">https://hdl.handle.net/1911/16362</a>. | en_US |
| dc.identifier.uri | https://hdl.handle.net/1911/16362 | 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 | Organic chemistry | en_US |
| dc.title | Studies on the synthesis and properties of cyclopropenes | 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 |
Files
Original bundle
1 - 1 of 1