Isomerically pure cis,cis,trans-1-pheny1-1,3,5-
heptatriene was prepared and cyclized. Ring closure
was followed by a 1,5 hydrogen shift, and the only product
observed was 1-phenyl -6-methyl -1,3-cyclohexadiene.
Rough first order rate constants for thermolysis and
the hydrogen shift were determined. Kinetic estimates
indicate that the report of disallowed product in a...
Part 1
The pyrolysis of cis-1-trimethylsiloxy-1-cyclopr opyl-3-cyclononene in the temperature range 285-350° is described. Instead
of siloxy-Cope rearrangement, undesired desiloxylation took place.
Part 2
Gas-phase pyrolytic rearrangement of 2-phenyl-1-trimethylsiloxy-1-vinylcyclononane was investigated in a static system
in the temperature range 213-330°. It was discovered that
three major products resulted: cis- and...
Both oxy-Cope and siloxy-Cope rearrangements involve
(1, 3) and (3, 3) sigrnatropic shifts. Both the concerted mechanism,
and the stepwise mechanism via a diradical intermediate are possible.
In a cyclic system such as cis-l-vinylcyclooct-3-en-l-ol, the thermal
rearrangement takes place preferably through a diradical intermediate.
At high temperature, the reaction also...
Certain 2- chioroethyl nitrosoureas have been demonstrated
to be highly specific inactivators of chymotrypsin
in vitro and glutathione reductase, both in vivo and in
isolated rat hepatocytes. The inactivation of glutathione
reductase in isolated hepatocytes resulted in an increased
sensitivity toward an adriamycin induced oxidative
challenge.
Prolonged incubation of 1-(2-chloroethyl)-3-([1-¹⁴...
This thesis examines the interconnection between the in vitro and in
vivo phosphorylation of rabbit muscle phosphofructokinase. The first goal
of the project was to show whether a novel site of rabbit muscle
phosphofructokinase that is subject to in vitro phosphorylation, serine 376,
may also become phosphorylated in vivo. Evidence...