Trimethylaluminum → 7-bromo-4-[(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)methyl]-6-methyl-3,4-dihydro-1,4-benzoxazepin-5(2H)-one

HRID 577571ノート

反応式

HRID 577571 の反応式
[Br:1][C:2]1[C:3]([CH3:26])=[C:4]([C:9]([O:12][CH2:13][CH2:14][NH:15][CH2:16][C:17]2[C:18](=[O:25])[NH:19][C:20]([CH3:24])=[CH:21][C:22]=2[CH3:23])=[CH:10][CH:11]=1)[C:5](OC)=[O:6].C[Al](C)C>O1CCOCC1>[Br:1][C:2]1[CH:11]=[CH:10][C:9]2[O:12][CH2:13][CH2:14][N:15]([CH2:16][C:17]3[C:18](=[O:25])[NH:19][C:20]([CH3:24])=[CH:21][C:22]=3[CH3:23])[C:5](=[O:6])[C:4]=2[C:3]=1[CH3:26]

参加物

4

反応物 2

HCID 16682925TrimethylaluminumHCID 86723798Methyl 3-bromo-6-(2-{[(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)methyl]amino}ethoxy)-2-methylbenzoate

生成物 1

HCID 867237977-bromo-4-[(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)methyl]-6-methyl-3,4-dihydro-1,4-benzoxazepin-5(2H)-one収率 29%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

To a solution of methyl 3-bromo-6-(2-{[(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)methyl]amino}ethoxy)-2-methylbenzoate (126c, 134 mg, 0.317 mmol) in 1,4-dioxane (1 mL) was added trimethylaluminum (2.0M in heptanes, 32.0 mg, 0.440 mmol). The reaction mixture was stirred at room temperature for 30 minutes, heated at 55° C. for 2 hours, and then 75° C. for 4 hours. The reaction mixture was cooled to room temperature, the solvent removed under vacuum, and the residue was stirred vigorously with EtOAc (25 mL) and 10% aq. solution of Rochell's salts. Once the mixture became homogeneous, the layers were separated and the organic layer was purified directly by column chromatography (silica gel, (7N NH3 in MeOH) in EtOAc) to give 7-bromo-4-[(4,6-dimethyl-2-oxo-1,2-dihydropyridin-3-yl)methyl]-6-methyl-3,4-dihydro-1,4-benzoxazepin-5(2H)-one (126d, 36 mg, 27% yield) as a light tan solid.

後処理

  1. temperatureheated at 55° C. for 2 hours
  2. wait75° C. for 4 hours
  3. temperatureThe reaction mixture was cooled to room temperature
  4. customthe solvent removed under vacuum
  5. stirringthe residue was stirred vigorously with EtOAc (25 mL) and 10% aq. solution of Rochell's salts
  6. customthe layers were separated
  7. customthe organic layer was purified directly by column chromatography (silica gel, (7N NH3 in MeOH) in EtOAc)

出典と根拠

ORDレコード
ord-c10bea724bbb4b0e9c2bb05e5badc837
出典データセット
uspto-grants-2015_05
特許番号
US09040515B2

反応ノート

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