Thermolysis of N-tetramethylpiperidinyl esters: homolytic fragmentation and induced decomposition
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Bibliographic record
Abstract
The esters PhCH(OT)CO 2 T (2), PhCH 2 CO 2 T (5), PhCO 2 T, (6), and 1-AdCO 2 T (7, Ad = 1adamantyl), T = 2,2,6,6-tetramethyl-N-piperidinyl, undergo thermal decomposition at 120 C in toluene with the formation of carboxylic acids, 2,2,6,6-tetramethylpiperidine (TH), and bibenzyl in all cases, indicative of the formation of 2,2,6,6-tetramethylpiperidinyl radicals, but excluding the formation of the radicals PhCH 2 CO 2 and 1-AdCO 2 . Qualitative kinetic measurements show that 5-7 react much faster than expected for rate-limiting bond-homolysis, suggesting the occurrence of induced decomposition. Addition of 2,6-di-tert-butyl-4-methylphenol (BHT) to the reaction of PhCH 2 CO 2 T in hexane accelerates the reaction, with a first-order dependence on [BHT], and leads to the formation of the characteristic dimers 9 and 10 from 2,6-di-tert-butyl-4methylphenoxyl radical (12). These reactions of the esters 5-7 are interpreted to occur by molecule-induced homolysis, in which a hydrogen atom from toluene or BHT is transferred to oxygen forming RCO 2 H and the 2,2,6,6-tetramethylpiperidinyl radical T in a concerted process. Comparable behavior is observed for reactions in chloroform. PhCH(OT)CO 2 T (2) is proposed to form an intermediate PhCH()CO 2 T (1) which gives -lactone 19. Density functional calculations are used to model the overall energy changes in these reactions.
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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 | 0.000 |
| 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 it