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Record W4207020154 · doi:10.1002/047084289x.rn02436

Hexafluoroisopropyl Sulfamate

2022· other· en· W4207020154 on OpenAlexaff
Jarrod W. Johnson, Matthew A. Sguazzin, Jakob Magolan

Bibliographic record

VenueEncyclopedia of Reagents for Organic Synthesis · 2022
Typeother
Languageen
FieldChemistry
TopicSynthesis and Catalytic Reactions
Canadian institutionsMcMaster University
Fundersnot available
KeywordsChemistryReagentAcetonitrileDimethylacetamideSolubilityCarbon-13 NMRProton NMRFormic acidMedicinal chemistryNuclear magnetic resonance spectroscopyNuclear chemistryOrganic chemistrySolvent

Abstract

fetched live from OpenAlex

[637772-38-4] C3H3F6NO3S (MW 247.11) InChI = 1S/C3H3F6NO3S/c4-2(5,6)1(3(7,8)9)13-14(10,11)12/h1H,(H2,10,11,12) InChIKey = MIEKENGUIASFSB-UHFFFAOYSA-N (a sulfamoylation reagent for the synthesis of sulfamates and sulfamides from alcohols and amines; a nitrogen source for N-atom transfer in CH insertions and aziridinations) Alternative Names: HFIPS; HfsNH2; 1,1,1,3,3,3-hexafluoro-2-propyl sulfamate. Physical Data: white solid; mp 52–55 °C.1 1H NMR (CDCl3): δ 5.18 (sept, 3JHF = 5.6 Hz, 1H), 5.18–5.09 (brs, 2H). 13C NMR (CDCl3): δ 120.1 (qq, 1JCF = 283 Hz, 3JCF = 3.7 Hz, 2C), 73.5 (sept, 2JCF = 35.3 Hz). 19F NMR (CDCl3): δ −73.67.1 Solubility: soluble in EtOAc, Et2O, THF, DMF, MeCN, and acetone; moderately soluble in CH2Cl2 and CDCl3; and poorly soluble in hexanes. HFIPS is also soluble in DMSO, MeOH, and EtOH, but the long-term stability of the reagent in these solvents has not been determined. Analysis of Reagent Purity: 1H NMR, 13C NMR, and/or 19F NMR. HFIPS has also been characterized by X-ray crystallographic analysis (CCDC 2059516).1 Preparative Methods: HFIPS is synthesized using a two-step, one-pot procedure from chlorosulfonyl isocyanate (CSI)2 and hexafluoroisopropanol (HFIP) (eq 1). The slow addition of formic acid to a solution of CSI in acetonitrile, which generates sulfamoyl chloride in situ, is followed by the slow addition of a solution of HFIP in dimethylacetamide (DMA) without additional base (Caution: Strong evolution of CO and CO2 gas upon addition; potential runaway kinetics in certain solvents on larger scales).3–5 High yields for HFIPS have been reported (83–100%) using a large excess CSI (3–4 equiv) relative to HFIP,6–11 but a more reliable and atom-economical procedure using only a modest excess of CSI (1.3 equiv) has been published (74%, 32-g scale).1 Note that DMA and NMP are superior solvents to DMF for this reaction, and that, using an additional amine base is detrimental.3,4 The reaction is quenched with a slow addition of water, and HFIPS is extracted with Et2O. After washing the ethereal extracts with water and brine, the removal of residual DMA is aided considerably by washing with aqueous LiCl (10% w/v). (1) Purification: HFIPS is isolated in high purity following an aqueous workup but can also be purified using flash chromatography (EtOAc/Hex) on silica gel if desired. It should be noted, however, that HFIPS can be difficult to visualize by TLC since it is resistant to most common TLC stains, but its presence can be inferred by negative staining with iodine.11 Handling, Storage, Precautions: Stable for extended periods at room temperature, but storage at lower temperatures is likely beneficial; less stable when stored with water or DMA impurities.

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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)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Not applicable · Consensus signal: Not applicable
GenreCandidate signal: Other · Consensus signal: Other
Teacher disagreement score0.443
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0010.001
Meta-epidemiology (broad)0.0010.001
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)0.4430.000

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 head0.227
Teacher spread0.217 · 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
Published2022
Admission routes1
Has abstractyes

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