Hydrolytic Decarboxylation of Carboxylic Acids and the Formation of Protonated Carbonic Acid
Bibliographic record
Abstract
Acid-catalyzed decarboxylation reactions of carboxylic acids should avoid formation of protonated carbon dioxide, a very high energy species. A potential alternative route parallels ester hydrolysis, with addition of water to the carboxyl group followed by protonation of the unsaturated leaving group and formation of protonated carbonic acid, a species that had been predicted to be a viable reaction intermediate. The hydrolytic mechanism for the decarboxylation of pyrrole-2-carboxylic acid is consistent with observed (12)C/(13)C kinetic isotope effects (1.010 +/- 0.001 at H(0) = -0.01 and 1.043 +/- 0.001 at H(0) = -2.6), solvent kinetic isotope effects (k(H(2))(O)/k(D(2))(O) = 2 at H(0) = 0.9; k(H(2))(O)/k(D(2))(O) = 1 at H(0) = -2.9), and activation parameters [DeltaH() = 23.5 kcal.mol(-1) and DeltaS() = 5.5 cal.deg(-1).mol(-1) at H(0) = -2.9]. Thus, the specific route for a decarboxylation process is a consequence of the nature of the potential carbanion (or its conjugate acid), the acidity of the medium and avoidance of formation of protonated carbon dioxide.
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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 | 0.001 |
| 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".