The relative rates of hydrogen atom abstraction from a series of
13 homoaryl and heteroarylmethanes by t-butoxy radical were determined at 70°C. The attacking radical was photochemically generated
from di-t-butyl peroxide. A relatively small range of relative rates
(factor of seven) has been found among the compounds studied. The
relative...
A study of the effects of structural modification at
the alpha position of ethyl 2-bromocarboxylates on their
rates of addition to two alkene pairs was undertaken. In
the competition between 3-propoxypropene and 1-octene at
70°, a 37% increase in selectivity was observed in going
from carboxylates generating primary radicals to...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis. The reaction involves exothermic
consumption of intramolecular double bonds via insertion
into a carbon metal sigma bond. This represents an intramolecular
example of the reaction type responsible for metal catalyzed polymerization
of olefins.
Organolithium reagents were found to cyclize...
The relative rates of hydrogen atom abstraction from a series of 13 homoaryl
and heteroarylmethanes by the nucleophilic undecyl radical, thermally generated
from lauroyl peroxide, were determined at 70 °C. A reactivity range of 15 was
obtained. Substantial differences in reactivity among isomers were found. The
relative reactivities of the...
A three part study involving aspects of radical properties of various
aromatic species was accomplished.
Experiments to ascertain the importance of geometric and electronic
effects on the intramolecular transfer of a pi-complexed radical to a terminal double bond
was performed. Several 4-aryl-1-butenes were reacted in competition with 1-undecene
with a...