Substituent effects in the intramolecular photoredox reactions of benzophenones in aqueous solution
Bibliographic record
Abstract
A number of α-hydroxy-3-benzylbenzophenones 7–11 have been synthesized for the purpose of studying the effect of a phenyl substituent on the intramolecular photoredox reaction of 3-(hydroxymethyl)benzophenone (5) discovered in our laboratory. This latter compound was found to undergo a unimolecular (formal) intramolecular redox reaction upon photolysis in aqueous acid that results in clean reduction of the benzophenone ketone (to secondary alcohol) and oxidation of the alcohol to aldehyde. Three of the phenyl-substituted compounds with simple phenyl (7), p-methylphenyl (8), and p-methoxyphenyl (9) were found to undergo the acid-catalyzed intramolecular photoredox reaction with the observation that 9 also undergoes a residual photoredox reaction that is not acid-mediated and may involve initial photoinduced electron transfer, which is supported by LFP data. The m-methoxyphenyl (10) compound did not undergo the reaction. The trend in observed relative reactivity may be partially rationalized by examining changes in molecular orbital coefficients observed in the calculated HOMOs and LUMOs. The photoredox reaction has also been applied twice in succession in a single compound 11, demonstrating that the photoredox reaction may be useful for sequential photoredox reactions in a multifunctional compound.Key words: intramolecular photoredox, acid catalysis, meta effect, benzophenone photochemistry.
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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 | 0.001 |
| 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".