The photoelectron spectra of a series of ketone
compounds have been investigated in the gas phase. Core
ionization energies were measured to probe the effects of
molecular size and connectivity number on core ionization
energies.
It was found that core ionization energies roughly
decrease with increasing connectivity number as expected....
An examination was made of some reactions involving a transfer
of carbon from boron to carbon. In the case of the reaction of
a C[subscript n] alkylorganoborane with dichlorocarbene the intermediate was
a C[subscript n]₊₁ chloroalkylorganoborane. Oxidation of this intermediate
yielded an homologous acid (33%) and the usual alcohol (66%)....
Steroid carbenes have been investigated as synthetic intermediates.
Basic decomposition of 4-en-3-one tosylhydrazones (and
other A-ring systems) gives varying amounts of 2, 4-dienes, and
solvent derived products with diglyme, heptane, tetrachloroethylene,
carbon tetrachloride, benzene and cyclohexene. A method for
separating complex product mixtures was developed and a study of
the...
New syntheses for 2-bicyclo(3.3.1)nonanone and 7-bicyclo-(3.3.1)nonen-2-one were developed. The saturated ketone was prepared
from phenol and acrylonitrile via a novel intramolecular
S[subscript N]2 cyclization process. A Friedel-Crafts cyclization of 3-(3-cyclohexenyl)propanoyl chloride permitted synthesis of the unsaturated
ketone from 4-cyclohexene carboxaldehyde. The formation of
the bicyclo(3.3.1)nonane rather than a bicyclo(3.2.2)nonane skeleton...
A facile route to bicyclo(2.1.1)hexanes was developed involving
the intramolecular photocyclization of 1, 5-hexadien-3-one to
bicyclo(2.1.1)hexan-2-one. A study of the chemistry of bicyclo-(2.1.1)hexan-2-one was undertaken. Deuterium exchange and borohydride
reduction demonstrated the strain present in the ketone.
Further evidence was obtained from the failure to introduce substituents
alpha to the...
Dihalocarbenes have been generated by thermal decomposition
of sodium trichloroacetate and tribromomethylphenylmercury, and
give mono dihalocyclopropyl adducts with steroid dienes. Such
compounds offer an easy starting point for the synthesis of unusual
derivatives of potential biological interest. Under the same conditions,
however, addition to non-conjugated double bonds does not
take...
Cyclopropylcyclobutene was prepared via the intermediate
dicyclopropylcarbinyl carbene which was generated by the thermal
decomposition of the sodium salt of dicyclopropylketone p-toluenesulfonylhydrazone.
The successive thermal isomerization of cyclopropylcyclobutene
to 2-cyclopropyl-1, 3-butadiene and to vinylcyclopentene
was studied. Kinetic data were obtained for the cyclopropylcyclobutene
to 2-cyclopropyl-1, 3-butadiene isomerization in the gas...
Quaternary Ammonium Compounds, Qams, are an important class of
chemicals which present interesting challenges to analysts. This thesis
reports results of investigations on uses of ion-pairing techniques for
separations and detection of Qams. Special apparatus for post-column
solvent extraction of liquid chromatographic eluates was developed as
part of this work....
Steroid organoboranes have been found to be useful synthetic
intermediates. Attempted pyrolyses, based on simple trialkylborane
cyclizations, have not yielded C-19 or C-18 functionalized steroids,
but have produced isomerized systems not otherwise available.
Thus, hydroboration of cholesterol followed by pyrolysis at
215° gives 31% of 2-cholestene-6α-ol and 49% of a...