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Record W2002661844 · doi:10.1021/ja039078g

Photoaddition of Water and Alcohols to the Anthracene Moiety of 9-(2‘-Hydroxyphenyl)anthracene via Formal Excited State Intramolecular Proton Transfer

2004· article· en· W2002661844 on OpenAlexaff
Mitchel Flegel, Matthew Lukeman, Lawrence A. Huck, Peter Wan

Bibliographic record

VenueJournal of the American Chemical Society · 2004
Typearticle
Languageen
FieldChemistry
TopicPhotochemistry and Electron Transfer Studies
Canadian institutionsUniversity of Victoria
Fundersnot available
KeywordsChemistryAnthraceneMoietyPhotochemistryIntramolecular forceFlash photolysisDeuteriumExcited stateSolventStereochemistryOrganic chemistryReaction rate constantKinetics

Abstract

fetched live from OpenAlex

The title compound undergoes efficient photoaddition of a molecule of a hydroxylic solvent (H(2)O, MeOH, (Me)(2)CHOH) across the 9- and 10-positions of the anthracene moiety to give isolable triphenylmethanol or triphenylmethyl ether type products. The reaction is believed to proceed via a mechanism involving water-mediated formal excited state intramolecular proton transfer (ESIPT) from the phenolic OH to the 10-position of the anthracene ring, generating an o-quinone methide intermediate that is observable by nanosecond laser flash photolysis, and is trappable with nucleophiles. A "water-relay" mechanism for proton transfer seems plausible but cannot be proven directly with the data available. Irradiation in deuterated solvents led to incorporation of one deuterium atom at the methylene position in the photoaddition product, and partial deuterium exchange of the 10-position of recovered starting material, consistent with the proposed formal excited state proton transfer mechanism. The deuterium exchange and photoaddition reach maximum quantum efficiency at approximately 5 M water (in CH(3)CN or CH(3)OH), with no reaction observed in the absence of a hydroxylic solvent, demonstrating the sensitivity of this type of ESIPT to solvent composition.

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 imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
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 score0.002
Threshold uncertainty score0.006

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0000.000
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)0.0020.000

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 head0.006
GPT teacher head0.226
Teacher spread0.220 · 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 source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
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

Citations65
Published2004
Admission routes1
Has abstractyes

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Same venueJournal of the American Chemical SocietySame topicPhotochemistry and Electron Transfer StudiesFrench-language works237,207