The photochemistry of indenyl alcohols and esters: Substituent effects on the competition between ion- and radical-derived products
Bibliographic record
Abstract
The photochemistry of the indenyl acetates 1 and pivalates 2, substituted with X = H, 5-CH 3 O, and 6-CH 3 O, have been examined in both methanol and cyclohexane. The precursor alcohols 3 were also found to be photoreactive. Although only radical-derived products were obtained in cyclohexane, both ion- and radical-derived products were formed in methanol. The absence of significant fluorescence emission from any of the substrates 1, 2, and 3 indicates that the excited singlet states are highly reactive. A mechanism is proposed for the ion-derived products that proceeds through direct heterolytic cleavage to give an indenyl cation carboxylate anion pair. The indenyl cations generated are anti-aromatic in the ground state and their efficient generation by this photochemical solvolysis is in sharp contrast to the very low reactivity of related ground-state substrates. For the pivalate esters 2, an excited-state migratory decarboxylation is proposed for the formation of tert-butyl derived products.Key words: ester photochemistry, indenyl cations, indenyl radicals.
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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 | 0.003 |
| 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 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".