Synthesis of Diazeniumdiolates from the Reactions of Nitric Oxide with Enolates
Why this work is in the frame
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Bibliographic record
Abstract
[reaction: see text] Reactions of nitric oxide with enolates derived from aliphatic methyl ketones containing alpha-methylene or alpha-methine groups and with enolates derived from alpha,alpha'-dimethylene or alpha,alpha'-dimethine ketones yield mono- or bis(diazeniumdiolate) products. Diazeniumdiolation occurs in the following order: alpha-methine > alpha-methylene > alpha-methyl. The amount of the base used alters the extent of diazeniumdiolation and the course of the reaction. Mono- and bis(diazeniumdiolate)-substituted methyl ketones are cleaved in the presence of excess base before and after the subsequent diazeniumdiolation of the alpha-methyl group. Similar to the trihalogenated methyl groups in the base-assisted halogenation reactions of methyl ketones, the bis(diazeniumdiolate)-substituted alpha-methylene and alpha-methyl groups act as leaving groups in the presence of excess base. The reaction of nitric oxide with a (approximately 20:80, cis/trans) mixture of 2,6-cyclohexananone yields the cis and trans isomers of 2,6-dimethylcyclohexanone-2,6-bis(diazeniumdiolate) in 12.9% and 57.6% yield. Single-crystal X-ray diffraction data determined for potassium cis-2,6-dimethylcyclohexanone-2,6-bis(diazeniumdiolate), cis-14b, reveal that the N(2)O(2-) substituent is planar with considerable delocalization of a double bond over the anionic four-atom group. Except for one of the diazeniumdiolate products, namely, potassium propanoate 2,2-bis(diazeniumdiolate), 8b, all are stable in neutral and basic aqueous media. Compound 8b slowly decomposes in neutral aqueous solution releasing nitrous oxide and nitric oxide gases but is stable in basic aqueous media. Differential scanning calorimetry data measured for the diazeniumdiolate products indicate that they decompose exothermally with most of them undergoing explosive decomposition at moderately high temperatures (181-274 degrees C).
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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