Bibliographic record
Abstract
It has been shown recently that many supposed reaction intermediates in aqueous media do not have lifetimes long enough for them to serve this purpose. Among these are oxygen-protonated species where the positive charge is not delocalized, primary and secondary carbocations, and the commonly written species H3O+ and HO–. This means that the mechanisms for many of the organic reactions that take place in aqueous media are in need of revision. This paper concerns the acid hydrolysis of simple ethers, many of which cannot form carbocations stable enough to exist in water. Rather than an A1 process in which an oxygen-protonated species dissociates into an alcohol and a carbocation, which is then quenched by water, or an A2 process in which a water molecule or another nucleophilic species assists in this, the mechanism for most ethers is a general-acid-catalyzed process in which proton transfer to oxygen is concerted with C–O bond cleavage in cases where a stable carbocation can exist, or additionally concerted with nucleophilic attack for those cases in which stable carbocation formation is not possible. All of the cases for which rate constant data could be found in the literature are analyzed and discussed in this paper, with the exception of the hydrolyses of several azoethers, where additional hydrolysis mechanisms are possible. These will be discussed in a subsequent paper.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.002 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.004 |
| Open science | 0.003 | 0.001 |
| Research integrity | 0.002 | 0.003 |
| Insufficient payload (model declined to judge) | 0.010 | 0.005 |
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".