Spontaneous Aqueous Defluorination of Trifluoromethylphenols: Substituent Effects and Revisiting the Mechanism
Bibliographic record
Abstract
Trifluoromethylphenols (TFMPs) are environmental contaminants that exist as transformation products of aryl-CF3 pharmaceuticals and agrochemicals. Their −CF3 moiety raises concerns as it may form problematic fluorinated transformation products such as the persistent pollutant trifluoroacetic acid (TFA). This study investigates the hydrolysis and spontaneous defluorination mechanisms of 2-TFMP, 3-TFMP, 4-TFMP, and 2-Cl-4-TFMP under environmentally relevant aqueous conditions, and under alkaline pH to investigate the mechanism of defluorination. 3-TFMP did not undergo hydrolysis. The other TFMPs reacted to primarily form the corresponding hydroxybenzoic acids and fluoride. High-resolution mass spectrometry identified a benzoyl fluoride intermediate in the hydrolysis of 4-TFMP and other dimer-like transformation products of the 4- and 2-Cl-4-TFMP. Density functional theory calculations revealed that the key defluorination step proceeds via an E1cb mechanism, driven by β-elimination. Experimental and computational results demonstrated substituent-dependent differences in reactivity, and the importance of the deprotonation of TFMPs for the hydrolysis reaction to proceed. These findings provide mechanistic insights into the complete defluorination of TFMPs and broader implications for the environmental defluorination of other PFAS.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 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".