Absolute reactivity of arylallyl carbocations
Bibliographic record
Abstract
Abstract A series of α ‐vinyl arylmethyl cations were generated and studied using nanosecond laser flash photolysis. Rate constants for the decay of the substituted α ‐vinyl arylmethyl cations were determined under solvolytic conditions in pure solvents and solvent mixtures of 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) and 2,2,2‐trifluoroethanol (TFE). In addition the absolute reactivity of the carbocations with added nucleophiles were obtained. The reactivities of the α ‐vinyl arylmethyl cations were then compared to the reactivities of the corresponding α ‐methyl, α ‐phenyl, and α ‐cyclopropyl arylmethyl cations. Hammett σ + plots of each of the series of carbocations were obtained and the substituent effects on carbocation reactivity analyzed. These data show that the influence of substituent on the reactivity of the α ‐vinyl carbocations was different from the substituents effects on the reactivity of the α ‐methyl, α ‐phenyl, and α ‐cyclopropyl series. Copyright © 2008 John Wiley & Sons, Ltd.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| 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) | 0.002 | 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 source (direct Gemma or distilled Codex), 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".