Mechanism of ipso aromatic substitution by reaction of aryloxy(methoxy)carbenes and diaryloxycarbenes with DMAD
Bibliographic record
Abstract
Some aryloxy(methoxy)carbenes and diaryloxycarbenes attack dimethyl acetylenedicarboxylate (DMAD) with aryl group transfer to an alkyne carbon of DMAD. In this study diaryloxycarbenes with different aryl groups that could be transferred competitively, were generated in the presence of DMAD to probe for the mechanism of that ipso aromatic substitution. It was found that a para electron-withdrawing substituent, relative to an electron-donating substituent, facilitated migration of an aryl group. Mechanisms in accord with these findings involve initial nucleophilic attack by the carbene at an alkyne carbon of DMAD. That step is followed by either nucleophilic, ipso attack on the aromatic ring or by electron transfer, from the side chain of the aromatic ring into the ring itself.Key words: aromatic substitution, diaryloxycarbene, DMAD, ipso, nucleophilic.
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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 | 0.000 |
| 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 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".