The α-effect in the S<sub>N</sub>Ar reaction of 1-(4-nitrophenoxy)-2,4-dinitrobenzene with anionic nucleophiles: effects of solvation and polarizability on the α-effect
Bibliographic record
Abstract
A kinetic study on SNAr reactions of 1-(4-nitrophenoxy)-2,4-dinitrobenzene (1a) with various anionic nucleophiles in 80 mol% water – 20 mol% DMSO at 25.0 °C is reported. The Brønsted-type plot for the reaction of 1a with a series of substituted phenoxides and HOO− results in an excellent linear correlation with βnuc = 1.17. However, OH− exhibits dramatic negative deviation from the Brønsted-type plot, while N3−, C6H5S−, and butane-2,3-dione monoximate (Ox−) deviate positively from linearity. HOO− is 680-fold more reactive than OH− but does not exhibit the α-effect. In contrast, Ox− is 166-fold more reactive than isobasic 4-Cl−C6H4O− and exhibits the α-effect. Differential solvation effects have been suggested to be responsible for the α-effect in this study, i.e., Ox− exhibits the α-effect, since it is 5.7 kcal/mol less strongly solvated than 4-Cl−C6H4O− in the reaction medium, while HOO− does not show the α-effect due to a strong requirement for partial desolvation before nucleophilic attack. The highly enhanced reactivity of polarizable N3− and C6H5S− and extremely decreased reactivity of nonpolarizable OH− are in accord with the hard–soft acid and base principle.
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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 | 0.000 |
| 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) | 0.001 | 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".