Sodium Carbonate → Tert-butyl (2e)-3-(4-amino-3-bromothieno[3,2-c]pyridin-7-yl)acrylate

HRID 17144

反応式

HRID 17144 の反応式
[Br:1][C:2]1[C:6]2[C:7]([NH2:12])=[N:8][CH:9]=[C:10](I)[C:5]=2[S:4][CH:3]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Na+].[Na+].[C:38]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])(=[O:41])[CH:39]=[CH2:40]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:12][C:7]1[C:6]2[C:2]([Br:1])=[CH:3][S:4][C:5]=2[C:10](/[CH:40]=[CH:39]/[C:38]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41])=[CH:9][N:8]=1

参加物

7

反応物 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 15458tert-Butyl acrylateHCID 184507913-Bromo-7-iodothieno[3,2-C]pyridin-4-amine

生成物 1

HCID 18451450Tert-butyl (2e)-3-(4-amino-3-bromothieno[3,2-c]pyridin-7-yl)acrylate収率 42.8%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

A solution of Example 21A (2.50 g, 7.04 mmol), PPh3 (0.370 g, 1.41 mmol), and Na2CO3 (1.49 g, 14.1 mmol) in DMF (35 mL) was treated with tert-butyl acrylate (2.00 mL, 14.1 mmol) and palladium(II)acetate (0.158 g, 0.704 mmol). The reaction was heated to 80° C. under an atmosphere of nitrogen for 16 hours. The reaction was cooled to ambient temperature and partitioned between ethyl acetate (100 mL) and brine. The organic phase was washed with brine (2×100 mL), dried (Na2SO4), filtered, and concentrated. The compound was purified by flash chromatography on silica gel using heptane/ethyl acetate (6:1) to (3:1) to provide the desired product (1.70 g, 3.01 mmol). 1HNMR (DMSO-d6, 400MHz) δ 8.24 (s, 1H), 7.94 (s, 1H), 7.62 (d, 1H), 7.17 (br s, 2H), 6.22 (d, 1H), 1.48 (s, 9H); MS m/e 355/357 (M+H)+.

後処理

  1. temperatureThe reaction was cooled to ambient temperature
  2. custompartitioned between ethyl acetate (100 mL) and brine
  3. washThe organic phase was washed with brine (2×100 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe compound was purified by flash chromatography on silica gel

出典と根拠

ORDレコード
ord-e1b0546f08de4b4e964df24b8397f34b
出典データセット
uspto-grants-2010_06
特許番号
US07737160B2

関連ノート

読み込み中…