Dimethylformamide → Di-tert-butyl [2-(ethoxycarbonyl)-1-benzothien-6-yl](fluoro)malonate

HRID 1172895

反応式

HRID 1172895 の反応式
[H-].[Na+].[C:3]([O:7][C:8](=[O:31])[CH:9]([C:17]1[CH:30]=[CH:29][C:20]2[CH:21]=[C:22]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[S:23][C:19]=2[CH:18]=1)[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])([CH3:6])([CH3:5])[CH3:4].CN(C=O)C.[B-](F)(F)(F)[F:38].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1>C1COCC1>[C:3]([O:7][C:8](=[O:31])[C:9]([C:17]1[CH:30]=[CH:29][C:20]2[CH:21]=[C:22]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[S:23][C:19]=2[CH:18]=1)([F:38])[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])([CH3:4])([CH3:5])[CH3:6]

参加物

6

反応物 4

HCID 6228DimethylformamideHCID 24758Sodium hydrideHCID 2724933SelectfluorHCID 59424236Di-tert-butyl [2-(ethoxycarbonyl)-1-benzothien-6-yl]malonate

生成物 1

HCID 59556415Di-tert-butyl [2-(ethoxycarbonyl)-1-benzothien-6-yl](fluoro)malonate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

To a suspension of sodium hydride (0.96 g, 24.0 mmol) in THF (75 mL) cooled to 0° C. was added a solution of di-tert-butyl[2-(ethoxycarbonyl)-1-benzothien-6-yl]malonate (described above) (9.66 g, 23.0 mmol) in THF (150 mL) under nitrogen. The resulting orange solution was stirred at 4° C. for 15 minutes. DMF (225 mL) was added followed by Selectfluor (8.15 g, 23.0 mmol). The reaction was warmed to ambient temperature and stirred for 4 hours under nitrogen. The reaction was quenched with ammonium chloride solution and partitioned between ethyl acetate and water. The organics were washed with water and brine, dried over magnesium sulfate, filtered and evaporated in vacuo. Purification by flash column chromatography (2-20% ethyl acetate/hexanes) gave a mixture of starting material and product. This was resubjected to above reaction conditions and purified in a similar manner to give a pale yellow solid. 1H NMR (DMSO-d6) δ 8.21 (s, 1H), 8.17 (s, 1H), 8.07 (d, J=8.8 Hz, 1H), 7.52 (d, J=9.1 Hz, 1H), 4.33 (q, J=7.3 Hz, 2H), 1.44 (s, 18H), 1.31 (t, J=7.0 Hz, 3H).

後処理

  1. temperatureThe reaction was warmed to ambient temperature
  2. stirringstirred for 4 hours under nitrogen
  3. customThe reaction was quenched with ammonium chloride solution
  4. custompartitioned between ethyl acetate and water
  5. washThe organics were washed with water and brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customPurification by flash column chromatography (2-20% ethyl acetate/hexanes)
  10. customgave
  11. additiona mixture of starting material and product
  12. customThis was resubjected to above reaction conditions
  13. custompurified in a similar manner
  14. customto give a pale yellow solid

出典と根拠

ORDレコード
ord-ddc6c742827d4b5797d9d4cbd4649564
出典データセット
uspto-grants-2010_11
特許番号
US07834034B2

関連ノート

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