Thermal Racemization of Substituted Indolinobenzospiropyrans: Evidence of Competing Polar and Nonpolar Mechanisms
Bibliographic record
Abstract
A series of 6-substituted indolinobenzospiropyrans were resolved by chiral stationary phase HPLC and rate constants k rac for their thermal racemization were measured by circular dichroism spectropolarimetry at 60 °C in three different solvents: cyclohexane, 90:10 hexanes/2-propanol, and acetonitrile. Results show that the spiropyrans undergo thermal racemization most rapidly in acetonitrile, with k rac values ranging from 9.3 × 10 - 5 to >5.0 × 10 - 3 s - 1, and least rapidly in cyclohexane, with k rac values ranging from 6.8 × 10 - 6 to 4.6 × 10 - 4 s - 1 . V-shaped plots of log k rac vs Hammett σ p constants in 90:10 hexanes/2-propanol and acetonitrile suggest that thermal racemization of the 6-substituted spiropyrans proceed via two competing mechanisms: a polar mechanism involving heterolytic C(sp 3 )−O bond cleavage with anchimeric assistance from the indoline nitrogen and a nonpolar electrocyclic ring opening mechanism with no anchimeric assistance from the indoline nitrogen. The outcome of this competition appears to be strongly influenced by solvent polarity: plots of log k rac vs σ p and σ - in cyclohexane show a near-linear correlation with negative slope, which is consistent with the nonpolar mechanism. However, an increase in solvent polarity results in a shift toward a linear correlation with positive slope, which is consistent with the polar mechanism.
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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 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".