The synthesis and structure of cyclopropenes and cycloproparenes

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dc.contributor.advisorBillups, W. Edwarden_US
dc.creatorHaley, Michael Marken_US
dc.date.accessioned2009-06-04T00:36:13Zen_US
dc.date.available2009-06-04T00:36:13Zen_US
dc.date.issued1991en_US
dc.description.abstractTetra-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. The following cyclopropenes were the target molecules, most of which were prepared successfully and in very good (55-85%) yields. The appropriate precursors were prepared by addition of a halo- or dihalocarbene to an alkenyltrimethylsilane. 1H,5H-Dicycloprop(b,h) anthracene (53) and 1H,4H-dicyclopropa(b,g) phenanthrene (54) were synthesized in 38% and 84% yield, respectively, by dehydrohalogenation with potassium t-butoxide in tetrahydrofuran at $-$20$\sp\circ$C. A key step in the syntheses was the Diels-Alder reaction of two equivalents of 1-bromo-2-chlorocyclopropene with the reactive 1,2,4,5- and 1,2,3,4-tetramethylenecyclohexanes.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) The corresponding dihydro derivatives 64 and 71 were prepared in 31% and 77% yield, respectively. The interesting cyclopropa(b) naphthalene derivative 69 was isolated in 57% yield. The starting compound for 69 was the major product from the reaction of 1-bromo-2-chlorocyclopropene with 1,2,3,4-tetramethylenecyclohexane.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) X-ray structural determinations were performed on cyclopropenes 48 and 49 and on cycloproparenes 24 and 40, in collaboration with Dr. Roland Boese at der Universitat Essen in Essen, Germany. The photoelectron spectrum of 49 was also obtained in collaboration with Prof. Rolf Gleiter at der Universitat Heidelberg in Heidelberg, Germany. These studies showed 49 to exhibit unusual bonding features.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)en_US
dc.format.extent251 p.en_US
dc.format.mimetypeapplication/pdfen_US
dc.identifier.callnoThesis Chem. 1991 Haleyen_US
dc.identifier.citationHaley, Michael Mark. "The synthesis and structure of cyclopropenes and cycloproparenes." (1991) Diss., Rice University. <a href="https://hdl.handle.net/1911/16445">https://hdl.handle.net/1911/16445</a>.en_US
dc.identifier.urihttps://hdl.handle.net/1911/16445en_US
dc.language.isoengen_US
dc.rightsCopyright 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.subjectOrganic chemistryen_US
dc.titleThe synthesis and structure of cyclopropenes and cycloproparenesen_US
dc.typeThesisen_US
dc.type.materialTexten_US
thesis.degree.departmentChemistryen_US
thesis.degree.disciplineNatural Sciencesen_US
thesis.degree.grantorRice Universityen_US
thesis.degree.levelDoctoralen_US
thesis.degree.nameDoctor of Philosophyen_US
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