A Study of the Preparation of Tricyclo[4,1,0,0³,⁷]heptane and the 6-Halofulvenes

Citation

Bruckner, Joseph Robert (1971) A Study of the Preparation of Tricyclo[4,1,0,0³,⁷]heptane and the 6-Halofulvenes. Master's thesis, California Institute of Technology. doi:10.7907/QQX0-NP82. https://resolver.caltech.edu/CaltechTHESIS:04202010-094744901

Abstract

Part I:
The literature synthesis, with some modifications, of tricyclo[ 4, 1, 0, 0^3,7]heptane was undertaken. While considerable difficulty was encountered in the final reaction involving a sodium borohydride reduction, far more successful results were obtained when lithium aluminum hydride was used instead as the reducing agent. The hydrocarbon can be stereospecifically deuterated at various points in the reaction sequence and once labeled, can be pyrolyzed and its products studied to determine the extent of orbital symmetry restrictions on the pyrolytic rearrangement process.

Part II:
In efforts to produce the mono- and diadducts of dichloro- and dibromocarbene to cyclopentadiene, it was found that the respective 6-halofulvenes were being produced instead. Depending upon the conditions used, varying amounts of halobenzene and 1, 1-dihalo-2, 2- dimethylcyclopropane could be produced as other major reaction products. The fulvenes were obtained in best yield using haloform as the dihalocarbene precursor and potassium tert-butoxide as the base. Ethyl trichloroacetate and phenyl (bromodichloromethyl) mercury were also used with various bases to generate dichlorocarbene, but these methods were unsuccessful in producing the 6-chlorofulvene.

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