Theoretical investigation of methoxide ion reaction on the 7-methyl-4,6-dinitrobenzofuroxan
Bibliographic record
Abstract
Reaction of the methoxide ion on the 7-methyl-4,6-dinitrobenzofuroxan (DNBF) 1 has been studied theoretically by means of DFT/B3LYP technique to interpret the kinetic–thermodynamic competition between the three possible compounds that are carbanion DNBF− 4 and the two complexed forms (2, 3) of the methoxide group in positions 5 and 7, respectively. Optimized geometry, nbo atomic charge distribution, thermodynamic/kinetic parameters (ΔrH°T, ΔrS°T, ΔrG°T, ΔH*, ΔS*, and ΔG*) and IRC path have been calculated for possible products and their transitional states using water as solvent. All obtained ΔrG°T are negative, ranging from −19.16 to −42.87 kcal mol−1 (1 cal = 4.184 J), indicating the possible observation of all products, but the experimenters only detected the anionic form DNBF−. Fukui indices, which were calculated by means of NBO atomic charge distribution, confirm the electrophilicity of the sites C5 and C7. Transition states barriers, ΔG*, are 14.97, 15.16, and 21.94 kcal mol−1 for the three possible products 2, 3, and 4, respectively, in water. As expected, the most stable compound is carbanion, but it also exhibits the highest activation barrier. If this situation formally engenders a double kinetic–thermodynamic competition, the very weak activation energy of the two complexes in C5 and C7 makes improbable the simultaneous detection of the three expected compounds.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.000 |
| Insufficient payload (model declined to judge) | 0.006 | 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".