Oxidation of secondary hydroperoxides via αC–H abstraction to form ketones and hydroxyl radicals: fluorene autoxidation as a model system
Bibliographic record
Abstract
Organic and biological molecules with relatively weak C–H bonds can react with O 2 via a free-radical reaction called autoxidation. The primary products of these peroxyl-radical-driven reactions are hydroperoxides, R 2 CHOOH. If autoxidation continues, the secondary oxidation of hydroperoxides is known to form ketones, R 2 C═O, but this mechanism is not well characterized. Importantly, we find that ketone formation produces a highly reactive hydroxyl radical, HO • . We can trap HO • using benzene as a solvent to form quantifiable amounts of phenol. Fluorene was chosen as a model system to study this secondary oxidation in great detail. Kinetic modeling allowed the measurement of rate constants for the primary and secondary autoxidation reactions as 11.3 and 25 mol L −1 s −1 , respectively. Density functional theory modeling likewise predicts a faster oxidation for the secondary autoxidation. This type of kinetic measurement and modeling approach could be useful to study the autoxidation of plastics, petrochemicals, and lipids.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".