The 3-cyclohexenyl carbinyl carbene species was formed by the
thermal decomposition of the p-toluenesulfonylhydrazone sodium
salt and by oxidation of the hydrazone. Several oxidizing agents
were studied. The products were investigated under aprotic and
protic conditions and at various temperatures. The diazocompound
was formed as an intermediate and found to...
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...
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...
Dihalocarbenes have been generated mainly by thermal decomposition
of sodium trihaloacetate and phenyl (trihalomethyl)mercury,
and give gem-dihalocyclopropyl adducts with various steroid olefins.
A new procedure involving the use of sealed tubes makes possible the
addition of dihalocarbenes to sterically hindered olefins. In this manner,
7-cholestenyl benzoate when treated with PhHgCC1₃...
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...
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...