In this thesis, I describe the development of new methods for synthesizing polycyclic aromatic hydrocarbons (PAHs). The new methods presented can be separated into two categories: solution phase methods and gas phase methods. The reactivity of novel PAHs toward electrophiles and an attempted synthesis of a conducting polymer will also be presented.
For the construction of C 3 and C 3h , triply annulated benzene derivatives, no method rivals the acid catalyzed aldol cyclotrimerization. However, this method has received little use on account of its unpredictability. Currently, Scott and coworkers are attempting to chemically synthesize the endcaps of carbon nanotubes, and a number of these planned synthetic strategies utilize the aldol cyclotrimerization. To make these syntheses successful, this reaction needed to be better understood so that its full power could be harnessed.
Fullerenes and other geodesic polyarenes possess a unique mode of reactivity not observed in flat polycyclic aromatic hydrocarbons, which is attack by electrophiles and carbeneoids at interior carbon atoms. We have used modern computational methods to identify flat PAHs that may possess the ability to undergo attack at their interior carbon atoms. Using our calculations as a guide, various large flat PAHs were synthesized, and their reactivities towards electrophiles and carbenoids were examined.
Currently, the field of conducting polymer research is extremely broad, with conducting polymers being used in microelectronics and organic photovoltaics. Our goal is to design a soluble polyacetylene that would be amenable to p- or n-doping; the structural motif chosen was acenaphthylene, and so the synthesis of a polymer that contained acenaphthylene as a repeating unit was undertaken.
Flash Vacuum Pyrolysis (FVP) is a method of synthesizing strained PAHs. The Scott laboratory has had great success using this technique to create Buckminsterfullerene (C 60 ), as well as other novel geodesic polyarenes. The work described will focus on new methods to form radicals in FVP, such as using heteroatoms (sulfur) in place of halogens, or the introduction of an external radical source.
