Comparative Study of the Reactivities of Substituted 3-(Benzoyl)benzyl Carbanions in Water and in DMSO
Bibliographic record
Abstract
Benzyl-substituted carbanions produced by photodecarboxylation of ketoprofen derivatives have been examined in basic aqueous and DMSO solutions. Product studies, combined with kinetic measurements from laser flash photolysis, have allowed the determination of absolute rate constants for protonation and intra-S(N)2 reactions leading to five- and six-membered ring cyclizations; the former are significantly faster. Many of the well-known trends in carbanion reactivity are placed on an absolute rate basis; thus, intra-S(N)2 are favored in polar nonprotic solvents, and the effect is larger for the more hindered carbanion centers. Protonation by water is slightly dependent on the nature of the carbanion center and is approximately 400 times faster in nonhydroxylic solvents, compared with bulk water. As expected, the reactivity for halide leaving groups follows the usual order of decreasing bond strengths, i.e., I(-) > Br(-) > Cl(-).
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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".