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)
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/16362 |
| Date | January 1990 |
| Creators | Lee, Gon-Ann |
| Contributors | Billups, W. E. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 120 p., application/pdf |
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