The Phototransposition in Acetonitrile and the Photoaddition of 2,2,2-Trifluoroethanol to the Six Isomers of Dimethylbenzonitrile
Bibliographic record
Abstract
The six dimethylbenzonitriles can be divided into two independent triads in their photochemical reactivity. The first triad is comprised of the 2,3-dimethyl, 3,4-dimethyl, and 2,6-dimethyl isomers (11-2,3, 11-3,4, and 11-2,6, respectively); the second triad is comprised of the 2,4-dimethyl, 2,5-dimethyl, and 3,5-dimethyl isomers (11-2,4, 11-2,5, and 11-3,5, respectively). In acetonitrile, phototransposition converts the members of one triad to other members of the same triad, although only 11-3,4 was reactive enough to have significant conversion approaching a steady-state composition. Irradiation in 2,2,2-trifluoroethanol (TFE) resulted in the formation of addition products, 6-cyano-X,Y-dimethylbicyclo[3.1. 0]hex-3-en-2-yl 2,2,2,-trifluoroethyl ethers, but in significant yield only from 11-3,4 of the first triad and 11-2,4 of the second triad. The 11-3,4 isomer gave seven major regio- and stereoisomers; the 11-2,4 isomer gave three different regio- and stereoisomers. These addition products were all explained by formation of bicyclo[3. 1.0]hex-3-en-1-yl cations resulting from protonation by TFE at C6 followed by nucleophilic trapping by TFE. From these and previous results on aromatic nitriles, a consistent mechanistic picture is obtained where the critical carbon in determining the products of the phototransposition and photoaddition reactions is the cyano substituted one.
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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) | 0.000 | 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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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".