Chlorotrimethylsilane → 9a-butyl-7-methoxymethoxy-4-methyl-3-trimethylsilyloxy-9,9a-dihydro-1H-fluorene

HRID 7866

反応式

HRID 7866 の反応式
[CH2:1]([C:5]12[CH2:17][CH2:16][C:15](=[O:18])[C:14]([CH3:19])=[C:13]1[C:12]1[C:7](=[CH:8][C:9]([O:20][CH2:21][O:22][CH3:23])=[CH:10][CH:11]=1)[CH2:6]2)[CH2:2][CH2:3][CH3:4].[Li+].CC([N-]C(C)C)C.C(=O)=O.CC(C)=O.Cl[Si:40]([CH3:43])([CH3:42])[CH3:41].C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O>[CH2:1]([C:5]12[CH2:17][CH:16]=[C:15]([O:18][Si:40]([CH3:43])([CH3:42])[CH3:41])[C:14]([CH3:19])=[C:13]1[C:12]1[C:7](=[CH:8][C:9]([O:20][CH2:21][O:22][CH3:23])=[CH:10][CH:11]=1)[CH2:6]2)[CH2:2][CH2:3][CH3:4]

参加物

8

反応物 5

HCID 6397ChlorotrimethylsilaneHCID 516892Sodium BicarbonateHCID 2724682Lithium diisopropylamideHCID 18522661Acetone cardiceHCID 219908939a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one

生成物 1

HCID 219909149a-butyl-7-methoxymethoxy-4-methyl-3-trimethylsilyloxy-9,9a-dihydro-1H-fluorene

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

A solution of 9a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (163 mg, 0.52 mmol) in anhydrous THF (2.5 mL) was cooled in an ice bath and stirred under a nitrogen atmosphere while 0.4M LDA in THF (1.9 mL, 0.78 mmol) was added by syringe. After stirring at 0° C. for 30 minutes, the solution was cooled to −78° C. (dry ice-acetone bath) and treated with chlorotrimethylsilane (0.100 mL, 0.78 mmol). The resulting mixture was allowed to slowly warm to room temperature, then stirred at room temperature overnight. The mixture was diluted with EtOAc (60 mL) and shaken with 5% aqueous NaHCO3 (30 mL). The aqueous phase was separated and extracted with more EtOAc (30 mL). The combined organics were washed with saturated brine, dried over MgSO4, filtered, and concentrated under vacuum to an oil (204 mg). The 1H NMR of this material showed a 9:1 mixture of 9a-butyl-7-methoxymethoxy-4-methyl-3-trimethylsilyloxy-9,9a-dihydro-1H-fluorene and starting material.

後処理

  1. additionwas added by syringe
  2. temperatureto slowly warm to room temperature
  3. stirringstirred at room temperature overnight
  4. customThe aqueous phase was separated
  5. extractionextracted with more EtOAc (30 mL)
  6. washThe combined organics were washed with saturated brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum to an oil (204 mg)
  10. additiona 9:1 mixture of 9a-butyl-7-methoxymethoxy-4-methyl-3-trimethylsilyloxy-9,9a-dihydro-1H-fluorene

出典と根拠

ORDレコード
ord-1359d29ce9324090968a6c78e5d5d25d
出典データセット
uspto-grants-2006_08
特許番号
US07087599B2

関連ノート

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