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1,2-Dibromopropane → Ethyl 6,7-dihydro-5H-pyrazolo[5,1-B][1,3]oxazine-3-carboxylate

HRID 1697460
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1697460
[CH2:1]([O:3][C:4]([C:6]1[C:7](=[O:11])[NH:8][NH:9][CH:10]=1)=[O:5])[CH3:2].C(=O)([O-])[O-].[K+].[K+].Br[CH2:19][CH:20](Br)[CH3:21]>CN(C)C=O>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[N:9][N:8]2[CH2:21][CH2:20][CH2:19][O:11][C:7]=12)=[O:5])[CH3:2]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

5

Edukt 3

HCID 65531,2-DibromopropaneHCID 11430Potassium CarbonateHCID 238933Ethyl 2,3-dihydro-3-oxo-1H-pyrazole-4-carboxylate

Produkt 1

HCID 52228126Ethyl 6,7-dihydro-5H-pyrazolo[5,1-B][1,3]oxazine-3-carboxylateAusbeute 58,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

3-Oxo-2,3-dihydro-1H-pyrazole-4-carboxylic acid ethyl ester (13.2 g, 84.5 mmol), potassium carbonate (50 g, 0.3 mol) and N,N-dimethylformamide (500 mL) were combined in a 250 mL round bottom flask, and the mixture was heated to 130° C. 1,2-Dibromo-propane (10.4 mL, 0.10 mol) was added. After 30 minutes, the mixture was partitioned between DCM and water. The aqueous layer was extracted with DCM and the combined organics were washed with brine, dried (Na2SO4), filtered and concentrated in vacuo. The yellow solid was purified by column chromatography (DCM/MeOH) to afford the ester (9.67 g, 58%) as a solid. 1H NMR (400 MHz, DMSO-d6) δ7.62 (s, 1H), 4.41-4.38 (m, 2H), 4.13 (q, 2H), 4.08 (t, 2H, J=6.03 Hz), 2.21-2.15 (m, 2H), 1.21 (t, 3H, J=7.09 Hz).

Aufarbeitung

  1. customthe mixture was partitioned between DCM and water
  2. extractionThe aqueous layer was extracted with DCM
  3. washthe combined organics were washed with brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe yellow solid was purified by column chromatography (DCM/MeOH)

Quellen und Nachweise

ORD-Eintrag
ord-834678615d694e158ca0aacc84ef59ae
Quelldatensatz
uspto-grants-2012_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08163901B2

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