Measuring Aromaticity with the Dimethyldihydropyrene Ring Current Probe. Experimental and Computational Studies of the Fulvenes and the Strongly Antiaromatic Cyclopentadienone Reveal Large Mills−Nixon-Type Bond Localization Effects. Synthesis of Fulvene-Fused Dihydropyrenes
Bibliographic record
Abstract
The synthesis of the methylfulvene- and phenylfulvene-annelated dihydropyrenes 10 and 22 from the cyclopentadiene-fused dihydropyrene 7 in 68% and 80% yields, respectively, are reported. However, the attempted formation of the parent fulvene-fused dihydropyrene 18 failed, both from the cyclopentadiene 7 with formaldehyde and from the cyclopentadienone 5 in Wittig-type reactions. Chemical shift data for the methylfulvene (35) and phenylfulvene (36)-fused dihydropyrenes 10 and 22 were used to estimate the reduction in the dihydropyrene nucleus aromaticity (DHPN) (relative to benzene fusion) in 10 and 22 (12-16% and 22-25% respectively). Calculations revealed that this reduction in diatropicity, contrary to the situation with benzene fusion, is not due to any aromaticity of the annelating fulvenes but instead is caused by Mills-Nixon-type effects. We conclude that methyl- and phenylfulvene are nonaromatic. An improved synthetic route to the cyclopentadienone 5 was found in an unprecedented cyclization of the trans-cinnamic acid analogue 29 in 80% yield. This enabled an X-ray structure of 5 to be obtained, for comparison to that of the saturated ketone 4. Even though crystals of 5 and 4 show diastereomeric disorder, when the average bond length data of cyclopentadienone 5 is compared with those of cyclopentenone 4 and the parent and benzo dihydropyrenes 6 and 33, it is clearly evident that 5 has the opposite bond-alternation pattern, consistent with a [4n] fused annulene. From the bond length data, cyclopentadienone has approximately 87% of the effect of a benzene ring on bond alternation, which is in reasonable agreement with the previously found NMR value (78%). Structure and nucleus-independent chemical shift calculations support these results.
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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) | 0.000 | 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) | 0.003 | 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 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".