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Record W2093425035 · doi:10.1139/v00-021

Radicals from fragmentation of benzyloxymethoxycarbenes in solution

2000· article· en· W2093425035 on OpenAlexvenueno aff
Nadine Merkley, Manal El-Saidi, John Warkentin

Bibliographic record

VenueCanadian Journal of Chemistry · 2000
Typearticle
Languageen
FieldChemistry
TopicRadical Photochemical Reactions
Canadian institutionsnot available
Fundersnot available
KeywordsChemistryCarbeneFragmentation (computing)PhotochemistryRadicalAcetoneMedicinal chemistryAzineOrganic chemistryCatalysis

Abstract

fetched live from OpenAlex

2-Benzyloxy-2-methoxy-5,5-dimethyl-Δ 3 -1,3,4-oxadiazolines, including the parent as well as p-substituted analogues, undergo thermolysis at 100°C in benzene to afford a mixture of products. Two primary fragmentations of the oxadiazolines were identified. The major pathway involves 1,3-dipolar cycloreversion to N 2 and the corresponding carbonyl ylides. The latter dissociate to acetone and the corresponding benzyloxy(methoxy)carbenes, which undergo fragmentation to ArCH 2 and MeOCO radical pairs that recombine to afford methyl arylacetates. Carbene dimers were not observed, showing that the fragmentation process is faster than carbene dimerization. A second fragmentation pathway observed for the oxadiazolines is an alternative cycloreversion to the corresponding benzyl methyl carbonate and 2-diazopropane. Products from diazopropane included acetone azine and, in some instances, traces of propene.Key words: benzyloxy(methoxy)carbene, carbene, radical pair, rearrangement.

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)0.000
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 score0.019
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 integrity0.0000.000
Insufficient payload (model declined to judge)0.0190.000

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 head0.010
GPT teacher head0.235
Teacher spread0.225 · 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

Citations16
Published2000
Admission routes1
Has abstractyes

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