Toluene → 8-Fluoro-N-methoxy-N-methyl-3-phenyl-3a,4-dihydro-3H-pyrazolo[5,1-c][1,4]-benzoxazine-2-carboxamide

HRID 1867253Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1867253
Cl.[CH3:2][NH:3][O:4][CH3:5].C[Al](C)C.[F:10][C:11]1[CH:12]=[CH:13][C:14]2[O:19][CH2:18][CH:17]3[CH:20](C4C=CC=CC=4)[CH:21]=[N:22][N:16]3[C:15]=2[CH:29]=1.CCC([O-])=[O:33].[C:35]1([CH3:41])[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1>ClCCl>[F:10][C:11]1[CH:12]=[CH:13][C:14]2[O:19][CH2:18][CH:17]3[CH:41]([C:35]4[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=4)[C:21]([C:20]([N:3]([O:4][CH3:5])[CH3:2])=[O:33])=[N:22][N:16]3[C:15]=2[CH:29]=1

Komponenten

6

Edukt 4

HCID 1140TolueneHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 16682925TrimethylaluminumHCID 866247908-Fluoro-3-phenyl-3a,4-dihydro-3H-pyrazolo(5,1-c)(1,4)benzoxazine 2-ethylcarboxylate

Produkt 1

HCID 730455398-Fluoro-N-methoxy-N-methyl-3-phenyl-3a,4-dihydro-3H-pyrazolo[5,1-c][1,4]-benzoxazine-2-carboxamide

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

A suspension of N-methylmethoxyamine hydrochloride (0.048 g, 0.485 mmol) in dichloromethane (6 mL) at 0° C. was treated with a solution of trimethylaluminum (0.48 mL of a 2.0 M soln in PhMe, 0.971 mmol) and stirred for 20 min. A solution of racemic ester (1-6) (0.150 g, 0.441 mmol) in dichloromethane (2 mL) was added. After stirring for 48 h, the reaction was quenched by the addition of satd. aq. NH4Cl and extracted with EtOAc (2×50 mL). The organic solution was dried over MgSO4, filtered, and concentrated. The residue was purified by flash chromatography (SiO2, 25% EtOAc/hexanes) to provide desired amide (1-7) as a racemic mixture. 1HNMR (500 MHz, CDCl3) δ 7.33-7.35 (m, 4H), 7.17 (m, 1H), 7.10 (m, 1H), 6.80-6.77 (m, 1H), 6.54 (m, 1H), 4.98 (d, J=12.2 Hz, 1H), 4.38 (m, 1H), 3.86-3.82 (m, 4H), 3.30 (br s, 1H) 2.04 (s, 3H) ppm.

Aufarbeitung

  1. stirringAfter stirring for 48 h
  2. customthe reaction was quenched by the addition of satd
  3. extractionaq. NH4Cl and extracted with EtOAc (2×50 mL)
  4. dry with materialThe organic solution was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (SiO2, 25% EtOAc/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-5a9ad0b06a554460bcbbbc36f0527dba
Quelldatensatz
uspto-grants-2009_12
Patentnummer
US07632833B2

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