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Record W2150937251 · doi:10.1139/v2012-060

Revised mechanism for the hydrolysis of ethers in aqueous acid

2012· article· en· W2150937251 on OpenAlexaffvenue
Robin A. Cox

Bibliographic record

VenueCanadian Journal of Chemistry · 2012
Typearticle
Languageen
FieldChemistry
TopicChemical Reaction Mechanisms
Canadian institutionsThe Scarborough Hospital
Fundersnot available
KeywordsCarbocationChemistryProtonationNucleophileDelocalized electronAqueous solutionConjugate acidPhotochemistryAcid catalysisSolvolysisSN1 reactionHydrolysisReaction rate constantMedicinal chemistryComputational chemistryOrganic chemistryCatalysisIon

Abstract

fetched live from OpenAlex

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 H 3 O + 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.

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 distilled prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesInsufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.007
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0010.000

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.

Opus teacher head0.014
GPT teacher head0.228
Teacher spread0.214 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations10
Published2012
Admission routes2
Has abstractyes

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