Diethyl Ether → HCID 58125491、化合物

HRID 1697463ノート

反応式

HRID 1697463 の反応式
CON(C)[C:4]([C:6]1[CH:7]=[N:8][N:9]2[CH2:14][CH2:13][CH2:12][O:11][C:10]=12)=[O:5].[CH3:16][Mg]Br.CCOCC>O1CCCC1>[N:8]1[N:9]2[C:10]([O:11][CH2:12][CH2:13][CH2:14]2)=[C:6]([C:4](=[O:5])[CH3:16])[CH:7]=1

参加物

5

反応物 3

HCID 3283Diethyl Ether2 回HCID 58125481HCID 58125481、化合物HCID 178418573HCID 178418573、化合物2 回

生成物 1

HCID 58125491HCID 58125491、化合物収率 82%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

A solution of 6,7-dihydro-5H-pyrazolo[5,1-b][1,3]oxazine-3-carboxylic acid methoxy-methyl-amide (9.02 g, 42.7 mmol) in tetrahydrofuran (300 mL) was cooled to 0° C. 3 M methylmagnesium bromide in ether (15.3 mL, 43 mmol) was added and the reaction was stirred at 0° C. for 30 minutes, then warmed to room temperature. Additional 3 M methylmagnesium bromide in ether (15.3 mL, 43 mmol) was added after 1 hour, and the mixture was stirred at room temperature overnight, then the volatiles were removed in vacuo. The residue was partitioned between EtOAc (100 mL) and saturated NaHCO3 solution (150 mL). The aqueous layer was extracted with EtOAc (2×100 mL), and the combined organic layers were washed with brine (3×50 mL), dried (Na2SO4), filtered and concentrated. Flash chromatography (0 to 4% MeOH in DCM) afforded the ketone (5.79 g, 82%) as a solid. 1H NMR (400 MHz, DMSO-d6) δ7.69 (s, 1H), 4.44 (t, 2H, J=5.25 Hz), 4.09 (t, 2H, J=6.10 Hz), 2.23 (s, 3H), 2.22-2.17 (m, 2H).

後処理

  1. temperaturewarmed to room temperature
  2. stirringthe mixture was stirred at room temperature overnight
  3. customthe volatiles were removed in vacuo
  4. customThe residue was partitioned between EtOAc (100 mL) and saturated NaHCO3 solution (150 mL)
  5. extractionThe aqueous layer was extracted with EtOAc (2×100 mL)
  6. washthe combined organic layers were washed with brine (3×50 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-1e464bfc4fce4477bf0eeff6b15e8570
出典データセット
uspto-grants-2012_04
特許番号
US08163901B2

反応ノート

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