Sodium Carbonate → ethyl 2-[4-(3,4-dihydro-2H-1-benzopyran-6-yl)-2,5-dimethyl thiophen-3-yl]-2-oxoacetate

HRID 591021ノート

反応式

HRID 591021 の反応式
C(=O)([O-])[O-].[Na+].[Na+].CC1(C)C(C)(C)OB([C:15]2[CH:16]=[C:17]3[C:22](=[CH:23][CH:24]=2)[O:21][CH2:20][CH2:19][CH2:18]3)O1.Br[C:27]1[C:28]([C:34](=[O:40])[C:35]([O:37][CH2:38][CH3:39])=[O:36])=[C:29]([CH3:33])[S:30][C:31]=1[CH3:32]>O.CN(C)C=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[O:21]1[C:22]2[CH:23]=[CH:24][C:15]([C:27]3[C:28]([C:34](=[O:40])[C:35]([O:37][CH2:38][CH3:39])=[O:36])=[C:29]([CH3:33])[S:30][C:31]=3[CH3:32])=[CH:16][C:17]=2[CH2:18][CH2:19][CH2:20]1

参加物

7

反応物 3

HCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70818387Ethyl (4-bromo-2,5-dimethyl-thiophen-3-yl)-oxo-acetate

生成物 1

HCID 70855185ethyl 2-[4-(3,4-dihydro-2H-1-benzopyran-6-yl)-2,5-dimethyl thiophen-3-yl]-2-oxoacetate収率 38%

試薬・触媒・溶媒 3

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

Under a nitrogen atmosphere, sodium carbonate (78 mg, 0.7 mmol), palladium tetrakis(triphenylphosphine) (81 mg, 0.07 mmol) and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (182 mg, 0.7 mmol) were added to a solution of ethyl (4-bromo-2,5-dimethyl-thiophen-3-yl)-oxo-acetate (17c) (200 mg, 0.69 mmol) in a mixture of water (3.5 mL) and N,N-dimethylformamide (11 mL). The mixture was heated at 110° C. for 1 hour. The mixture was then cooled at room temperature, concentrated in vacuo and water (30 mL) was added. The aqueous layer was extracted with ethyl acetate (2×30 mL). The organic layer was washed with brine (30 mL), dried over sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 80/20) to afford the desired product (17d) as a white solid (90 mg, 0.26 mmol, 38%).

後処理

  1. temperatureThe mixture was then cooled at room temperature
  2. concentrationconcentrated in vacuo and water (30 mL)
  3. additionwas added
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×30 mL)
  5. washThe organic layer was washed with brine (30 mL)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 80/20)

出典と根拠

ORDレコード
ord-3bbb51847c4340ec983f0f88e6a00aaf
出典データセット
uspto-grants-2016_01
特許番号
US09238026B2

反応ノート

読み込み中…