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Record W2018139764 · doi:10.1002/poc.1484

Absolute reactivity of arylallyl carbocations

2008· article· en· W2018139764 on OpenAlex

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenueJournal of Physical Organic Chemistry · 2008
Typearticle
Languageen
FieldChemistry
TopicChemical Reaction Mechanisms
Canadian institutionsDalhousie University
Fundersnot available
KeywordsCarbocationChemistryReactivity (psychology)SubstituentFlash photolysisSolvolysisNucleophilePhotochemistryMedicinal chemistryReaction rate constantSolvent effectsSolventComputational chemistryOrganic chemistryKineticsHydrolysisCatalysis

Abstract

fetched live from OpenAlex

Abstract A series of α ‐vinyl arylmethyl cations were generated and studied using nanosecond laser flash photolysis. Rate constants for the decay of the substituted α ‐vinyl arylmethyl cations were determined under solvolytic conditions in pure solvents and solvent mixtures of 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) and 2,2,2‐trifluoroethanol (TFE). In addition the absolute reactivity of the carbocations with added nucleophiles were obtained. The reactivities of the α ‐vinyl arylmethyl cations were then compared to the reactivities of the corresponding α ‐methyl, α ‐phenyl, and α ‐cyclopropyl arylmethyl cations. Hammett σ + plots of each of the series of carbocations were obtained and the substituent effects on carbocation reactivity analyzed. These data show that the influence of substituent on the reactivity of the α ‐vinyl carbocations was different from the substituents effects on the reactivity of the α ‐methyl, α ‐phenyl, and α ‐cyclopropyl series. Copyright © 2008 John Wiley & Sons, Ltd.

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.

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)0.000
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 score0.009
Threshold uncertainty score0.999

Codex and Gemma teacher scores by category

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 integrity0.0000.001
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 head0.012
GPT teacher head0.231
Teacher spread0.219 · 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