Ethyl Acetate → Tyclopyrazoflor

HRID 57102

Reaktionsgleichung

Reaktionsgleichung von HRID 57102
[Cl:1][C:2]1[C:6]([NH:7][CH2:8][CH3:9])=[CH:5][N:4]([C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[N:3]=1.C(OCC)(=O)C.C(=O)(O)[O-].[Na+].[F:27][C:28]([F:38])([F:37])[CH2:29][CH2:30][S:31][CH2:32][CH2:33][C:34](Cl)=[O:35]>O>[Cl:1][C:2]1[C:6]([N:7]([CH2:8][CH3:9])[C:34](=[O:35])[CH2:33][CH2:32][S:31][CH2:30][CH2:29][C:28]([F:38])([F:37])[F:27])=[CH:5][N:4]([C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[N:3]=1

Komponenten

6

Edukt 4

HCID 8857Ethyl AcetateHCID 516892Sodium BicarbonateHCID 674989573-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amineHCID 867006283-((3,3,3-Trifluoropropyl)thio)propanoyl chloride

Produkt 1

HCID 86700627Tyclopyrazoflor

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

A 100 mL three-neck round bottom flask was charged with 3-chloro-N-ethyl-1-(pyridine-3-yl)-1H-pyrazol-4-amine (5.00 g, 22.5 mmol) and ethyl acetate (50 mL). Sodium bicarbonate (4.72 g, 56.1 mmol) was added, followed by dropwise addition of 3-((3,3,3-trifluoropropyl)thio)propanoyl chloride (5.95 g, 26.9 mmol) at <20° C. for 2 hours, at which point HPLC analysis indicated that the reaction was complete. The reaction was diluted with water (50 mL) (off-gassing) and the layers separated. The aqueous layer was extracted with ethyl acetate (20 mL) and the combined organic layers were concentrated to dryness to afford a light brown solid (10.1 g, quantitative). A small sample of crude product was purified by flash column chromatography using ethyl acetate as eluent to obtain an analytical sample: mp 79-81° C.; 1H NMR (400 MHz, DMSO-d6) δ 9.11 (d, J=2.7 Hz, 1H), 8.97 (s, 1H), 8.60 (dd, J=4.8, 1.4 Hz, 1H), 8.24 (ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.60 (ddd, J=8.4, 4.7, 0.8 Hz, 1H), 3.62 (q, J=7.2 Hz, 2H), 2.75 (t, J=7.0 Hz, 2H), 2.66-2.57 (m 2H), 2.57-2.44 (m, 2H), 2.41 (t, J=7.0 Hz, 2H), 1.08 (t, J=7.1 Hz, 3H). EIMS m/z 406 ([M]+).

Aufarbeitung

  1. customthe layers separated
  2. extractionThe aqueous layer was extracted with ethyl acetate (20 mL)
  3. concentrationthe combined organic layers were concentrated to dryness
  4. customto afford a light brown solid (10.1 g, quantitative)
  5. customA small sample of crude product was purified by flash column chromatography
  6. customto obtain an analytical sample

Quellen und Nachweise

ORD-Eintrag
ord-934aacd11e9546d39b51f36290555141
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09434712B2

Verknüpfte Notizen

Wird geladen…