Pyrazinyl- and pyrimidinylketenes, bisketenes, and ylides: direct observation and nucleophilic reactivity
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Pyrazinylketene (9) and 4-pyrimidinylketene (11), identified by their IR absorption at 2128 and 2130 cm −1 , respectively, are formed in CH 3 CN as transient intermediates by photolysis of the corresponding diazoketones. The corresponding ylides 10 and 12 are formed concurrently as longer-lived intermediates identified by their distinctive IR and UV absorption. Reactions of 2-pyridylketene and of 9 and 11 with diethylamine form initial amide enol intermediates leading to dihydroheteroarene intermediates and then to amides, whereas amide enols are not observed in reactions with n-butylamine. Reactions with water give observable dihydroheteroarenes. 2,5-Bis(ketenyl)pyrazine (33) is formed by photolysis of 2,5-bis(diazoacetyl)pyrazine (32) together with the corresponding bis(ylide) 35. The latter is calculated to have two geometrically isomeric structures (bond-stretch isomers) with similar energies, one with a central six-membered aromatic ring and another with a 10-pi electron aromatic system.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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