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Record W2769704305 · doi:10.1002/047084289x.rn01915

Spiro[3<i>H</i>-diazirine-3,2′-tricyclo[3.3.1.1]decane]

2016· reference-entry· en· W2769704305 on OpenAlexaff
Yoann Schneider, Claude Y. Legault

Bibliographic record

VenueEncyclopedia of Reagents for Organic Synthesis · 2016
Typereference-entry
Languageen
FieldChemistry
TopicChemical Reaction Mechanisms
Canadian institutionsUniversité de Sherbrooke
Fundersnot available
KeywordsChemistryDiazirineAdamantaneHydroaminationTetramethylureaSolventOrganic chemistryStereochemistry

Abstract

fetched live from OpenAlex

Spiro[3H-diazirine-3,2(1tricyclo[3.3.1.1]decane] [41736-95-2] C10H14N2 (MW 162.23) InChI = 1S/C10H14N2/c1-6-2-8-4-7(1)5-9(3-6)10(8)11-12-10/h6-9H,1-5H2 InChIKey = PNVXTJMLAFYDOJ-UHFFFAOYSA-N (carbene precursor, electrophilic nitrogen source) Alternate Names: 2-adamantane-2,3′-[3H]-diazirine; diazirine adamantylidene; spiro[1,2-diazirine-3,2′-adamantane]; adamantane-2-spiro-3′-diazirine; adamantanone diazirine; adamantane diazirine; aziadamantane. Physical Data: mp 132–134 °C. Solubility: Soluble in most organic solvents. Form Supplied in: white solid. Analysis of Reagent Purity: 1H NMR (300 MHz, CDCl3) δ 2.10–2.04 (m, 6H), 1.82–1.75 (m, 6H), 0.65 (s, 2H). Preparative Methods: not commercially available. Aziadamantane was first synthesized in 1973.1 It is obtained in two steps from adamantanone.2 Adamantanone is first stirred with ammonia in methanol (25% w/v) for 45 min at −10 °C. Hydroxylamine-O-sulfonic acid (1.5 equiv) in 10 mL of methanol is then added dropwise. The mixture is stirred for 18 h at 4 °C and the solvent is removed by evaporation. The solid residue is extracted with CH2Cl2. The organic phase is then extracted with a 2N aq. H2SO4 solution. The aqueous phase is made alkaline with a 2N aq. NaOH solution and extracted with CH2Cl2. The organic phase is dried over K2CO3, filtered, and evaporated under reduced pressure to give the crude diaziridine (82%). It is used in the next step without further purification. A solution of CrO3 (1.5 equiv) in 2N aq. H2SO4 is added dropwise over 20 min to a vigorously stirred diaziridine suspension in acetone cooled at 0 °C. The resulting solution is then stirred at room temperature for 40 min. The mixture is poured onto ice and the precipitated product is extracted with pentane. The organic phase is washed sequentially with H2O, 5% aq. Na2CO3, and H2O, and then dried over Na2SO4. The solvent is evaporated and the crude is purified on a short silica column (pentane elution, 90% yield). Alternatively, an aqueous sodium hypochlorite solution can be used for the oxidation of the diaziridine to diazirine (99% yield), without the need for further purification.3 Handling, Storage, and Precautions: while no explosion of the title compound has been reported, it is advised to handle this product with caution, due to reported explosion of other diazirines.4, 5

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)0.004
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Research integrity, Insufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Not applicable · Consensus signal: none
GenreCandidate signal: Other · Consensus signal: Other
Teacher disagreement score0.743
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.004
Meta-epidemiology (narrow)0.0010.001
Meta-epidemiology (broad)0.0020.001
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0010.001
Insufficient payload (model declined to judge)0.0170.000

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 head0.016
GPT teacher head0.250
Teacher spread0.234 · 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 designNot applicable
Domainnot available
GenreOther

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".

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Citations0
Published2016
Admission routes1
Has abstractyes

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