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Título: Sulfur functionalized cubane and related derivatives
Autores: Priefer, Ronny
Fecha: 2002
Publicador: McGill University - MCGILL
Fuente:
Tipo: Electronic Thesis or Dissertation
Tema: Chemistry, Organic.
Descripción: Chapter one of this thesis reviews some work on cubane, from its initial synthesis by Eaton in 1964, to the recent studies of explosive and medicinal applications. Considering the wide variety of compounds that have been synthesized, it is curious that sulfur functionalized cubane has received virtually no attention.
Chapter two discusses the synthesis of cubanethiol, dicubyl disulfide, and a range of derivatives. Dicubyl disulfide possesses the shortest C-S bond length of any reported molecule where the carbon is sp3 hybridized. Calculations have confirmed that this apparently results from the high s-character that the external bonds of cubane possess. All four of the stable, oxidized versions of dicubyl disulfide have been prepared, as well as two trityl cubyl polysulfides.
In Chapter three, new synthetic pathways for the synthesis of cubylcarbinol have been established. One key step is the "two-in-one reaction" that performs the reduction of the carboxylic acid, as well as dehalogenation of 4-iodocubanecarboxylic acid using a single reagent to afford cubylcarbinol. This pathway increases the overall yield for obtaining cubylcarbinol, as well as being more economical.
Chapter four describes the work carried out on cubane-containing dialkoxy disulfides. The synthesis of two dialkoxy disulfides from cubylcarbinols was accomplished. The S2 liberation ability of these species was also investigated, and these represent the first non-benzylic dialkoxy disulfides that deliver trappable S2. In addition, a study of the previously unknown rearrangement/oxidation of these molecules to sulfites has been carried out.
In Chapter five, a thorough study of the reactivity of a vinyl cubane compound towards polymerization was performed. The subsequent cage opening and rearrangement to a styrene derivative, to our knowledge, is the first example of this kind known to occur without the assistance of a rhodium catalyst. In addition, cubane-containing norbornene polymers have been successfully synthesized. These represent the first examples of polymers that have a cubane tethered to the polymer backbone. It appears that this type of functionality does not impair solubility, which is the major problem associated with all other attempts to obtain cubane-based polymers.
Idioma: en