Hydrochloric Acid → (2SR,9aSR)-2-allyl-9a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one

HRID 7868

反応式

HRID 7868 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+].[CH3:25][CH:26]([N-]C(C)C)[CH3:27].C(=O)=O.CC(C)=O.C(Br)C=C.Cl>C1COCC1.CCOC(C)=O>[CH2:27]([CH:16]1[C:15](=[O:18])[C:14]([CH3:19])=[C:13]2[C:5]([CH2:1][CH2:2][CH2:3][CH3:4])([CH2:6][C:7]3[C:12]2=[CH:11][CH:10]=[C:9]([O:20][CH2:21][O:22][CH3:23])[CH:8]=3)[CH2:17]1)[CH:26]=[CH2:25]

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 7841Allyl bromideHCID 2724682Lithium diisopropylamideHCID 18522661Acetone cardiceHCID 219908939a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one

生成物 1

HCID 67401390(2SR,9aSR)-2-allyl-9a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

A solution of 9a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (230 mg, 0.73 mmol) in anhydrous THF (3.8 mL) was cooled in an ice bath, stirred under a nitrogen atmosphere, and treated with freshly prepared 0.4M LDA in THF (2.2 mL, 0.88 mmol). The resulting solution was stirred at 0° C. for 30 minutes, then cooled to −78° C. (dry ice-acetone bath) and treated with allyl bromide (0.316 mL, 3.65 mmol). The reaction mixture was allowed to gradually warm to room temperature then stirred at room temperature overnight. The mixture was diluted with EtOAc (60 mL) and shaken with 1N HCl (35 mL). The aqueous phase was extracted with EtOAc (20 mL) and the combined organics were washed with 5% NaHCO3 and brine, dried over MgSO4, filtered, and concentrated under vacuum to a yellow oil. The crude product was purified by preparative layer chromatography on three 0.1×20×20 silica gel GF plates using 4:1 hexanes-EtOAc as developing solvent. The UV visible band at Rf 0.44-0.56 was eluted with EtOAc and the eluant evaporated under vacuum to afford (2SR,9aSR)-2-allyl-9a-butyl-7-methoxymethoxy-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (193 mg) as an oil.

後処理

  1. stirringThe resulting solution was stirred at 0° C. for 30 minutes
  2. stirringthen stirred at room temperature overnight
  3. extractionThe aqueous phase was extracted with EtOAc (20 mL)
  4. washthe combined organics were washed with 5% NaHCO3 and brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum to a yellow oil
  8. customThe crude product was purified by preparative layer chromatography on three 0.1×20×20 silica gel GF plates
  9. washThe UV visible band at Rf 0.44-0.56 was eluted with EtOAc
  10. customthe eluant evaporated under vacuum

出典と根拠

ORDレコード
ord-6135e02ccc8a47dd9175ba392412cef1
出典データセット
uspto-grants-2006_08
特許番号
US07087599B2

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