Fragmentation of α-acyloxy and α-alkoxycarbonyloxy Radicals
Author Information
Author(s): Curran Dennis P, Turner Tiffany R
Primary Institution: University of Pittsburgh
Hypothesis
Do α-acyloxy and α-alkoxycarbonyloxy radicals fragment to form acyl and alkoxycarbonyl radicals?
Conclusion
The study found that the fragmentation of α-acyloxy and α-alkoxycarbonyloxy radicals is very slow and may not be competitive in radical chain reactions.
Supporting Evidence
- Only traces of ketone 15 were detected in the reduction of 11b even at very low concentrations.
- A conservative upper limit for the fragmentation of this type of radical at 80°C is <103 s-1.
- Small but variable amounts of ketone 15 (7–16%) were produced during cyclizations of 11b.
Takeaway
The researchers wanted to see if certain radicals could break apart to form new ones, but they found that this happens very slowly, making it not very useful for making new chemicals.
Methodology
The study used competition kinetics to isolate the fragmentation reaction of radicals generated from stable precursors.
Limitations
The study's results suggest that the fragmentation reactions are too slow to be useful in practical applications.
Digital Object Identifier (DOI)
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