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Oxidative Ring-Opening of Aromatics: Decomposition\nof Biphenyl Carboxylic Acids and Zinc Biphenyl Carboxylates

2017· article· en· W6884327557 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

VenueFigshare · 2017
Typearticle
Languageen
FieldMaterials Science
TopicSynthesis and properties of polymers
Canadian institutionsUniversity of Alberta
Fundersnot available
KeywordsDecarboxylationBiphenylOxidative decarboxylationDecompositionThermal decompositionCarboxylic acidZinc

Abstract

fetched live from OpenAlex

Ring-opening\nconversion of multinuclear aromatics can be used to\nupgrade heavy aromatic oils to lighter products, and it is usually\nperformed reductively with H<sub>2</sub>. Oxidative ring-opening is\nan alternative strategy that involves three steps: (i) oxidation of\nmultinuclear aromatics to quinonoids, (ii) further oxidation and ring-opening\nto produce aromatic carboxylic acids, and (iii) decarboxylation of\naromatic carboxylic acids. In the last step, decomposition by ketonization\nis an undesirable side reaction that leads to a ring-closed product.\nSelectivity control during aromatic carboxylic acid decomposition\nwas investigated using biphenyl-2-carboxylic acid, biphenyl-2,2′-dicarboxylic\nacid, zinc­(II) biphenyl-2-carboxylate, and zinc­(II) biphenyl-2,2′-dicarboxylate.\nThe reaction networks of thermal decomposition of the aromatic carboxylic\nacids were determined. Decomposition of biphenyl-2-carboxylic acid\ntook place mainly by decarboxylation to produce biphenyl, dehydration\nand ring-closure to produce fluorenone, and the formation of diphenic\nanhydride as intermediate product leading to fluorenone. Decomposition\nof biphenyl-2,2′-dicarboxylic acid proceeded through decarboxylation\nto biphenyl-2-carboxylic acid as intermediate, as well as two seemingly\nrelated pathways, leading to the formation of a hydroxy-fluorenone\nand a cyclic trione. Over the temperature range from 340 °C to\n400 °C, thermal decomposition invariably resulted in a higher\nketonization than decarboxylation selectivity. Decomposition of the\nanalogous zinc carboxylates demonstrated that ketonization could be\nsuppressed and the most abundant products were biphenyl > fluorenone\n> fluorene. It was possible to achieve a biphenyl (decarboxylation)\nto fluorenone (ketonization) selectivity ratio of 17:1 during batch\nreactor decomposition of zinc­(II) biphenyl-2,2′-dicarboxylate\nat 380 °C. Reaction stoichiometry indicated that water should\naffect selectivity, which is consistent with observations in the literature,\nbut this aspect was not investigated further.

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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 score0.045
Threshold uncertainty score0.966

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 science0.0010.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0350.000

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 head0.038
GPT teacher head0.282
Teacher spread0.244 · 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