Hexane → 4-bromo-9a-butyl-3-methylene-2,3,9,9a-tetrahydro-1H-fluoren-7-ol

HRID 7833

反応式

HRID 7833 の反応式
[Li][CH2:2]CCC.CCCCCC.[Br:12][C:13]1[C:14](=O)[CH2:15][CH2:16][C:17]2([CH2:27][CH2:28][CH2:29][CH3:30])[C:25]=1[C:24]1[C:19](=[CH:20][C:21]([OH:26])=[CH:22][CH:23]=1)[CH2:18]2>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[Br:12][C:13]1[C:14](=[CH2:2])[CH2:15][CH2:16][C:17]2([CH2:27][CH2:28][CH2:29][CH3:30])[C:25]=1[C:24]1[C:19](=[CH:20][C:21]([OH:26])=[CH:22][CH:23]=1)[CH2:18]2

参加物

6

反応物 3

HCID 8058HexaneHCID 98841384-Bromo-9a-butyl-7-hydroxy-1,2,9,9a-tetrahydro-fluoren-3-oneHCID 178418339Butyllithium

生成物 1

HCID 99674314-bromo-9a-butyl-3-methylene-2,3,9,9a-tetrahydro-1H-fluoren-7-ol

試薬・触媒・溶媒 2

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

A suspension of methyltriphenylphosphonium bromide (373 mg, 1.04 mmol) in anhydrous tetrahydrofuran (2 mL) was cooled in an ice bath and stirred under a nitrogen atmosphere while 2.5 N nBuLi in hexane (0.36 mL, 0.90 mmol) was added by syringe. The mixture was stirred at 0° C. for 10 minutes to complete formation of the methylenetriphenylphosporane reagent. A solution of 4-bromo-9a-butyl-7-hydroxy-1,2,9,9a-tetrahydro-fluoren-3-one (50 mg, 0.15 mmol) in tetrahydrofuran (1 mL) was added to the reaction mixture and the ice bath was removed. The resulting mixture was stirred at room temperature for 3.2 hours, then at 50° C. for 1.5 hour, and finally at room temperature for an additional 17 hours. The mixture was partitioned between saturated aqueous NH4Cl (5 mL) and EtOAc (9 mL). The organic phase was acidified with 2N HCl (0.2 mL), washed with brine (4 mL), dried over MgSO4, filtered, and evaporated under vacuum to an oil (90. mg). The crude product was purified by preparative layer chromatography on a 0.1×20×20 cm silica gel GF plate using 3:1 hexanes-EtOAc as developing solvent. The UV visible band at Rf 0.50-0.63 was eluted with EtOAc. The eluant was concentrated under vacuum to a residue which was lyophilized from benzene to afford 4-bromo-9a-butyl-3-methylene-2,3,9,9a-tetrahydro-1H-fluoren-7-ol.

後処理

  1. temperaturewas cooled in an ice bath
  2. additionwas added by syringe
  3. customthe ice bath was removed
  4. stirringThe resulting mixture was stirred at room temperature for 3.2 hours
  5. waitat 50° C. for 1.5 hour
  6. waitfinally at room temperature for an additional 17 hours
  7. customThe mixture was partitioned between saturated aqueous NH4Cl (5 mL) and EtOAc (9 mL)
  8. washwashed with brine (4 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. customevaporated under vacuum to an oil (90. mg)
  12. customThe crude product was purified by preparative layer chromatography on a 0.1×20×20 cm silica gel GF plate
  13. washThe UV visible band at Rf 0.50-0.63 was eluted with EtOAc
  14. concentrationThe eluant was concentrated under vacuum to a residue which

出典と根拠

ORDレコード
ord-c1e4715ed61c463392456f127089a013
出典データセット
uspto-grants-2006_08
特許番号
US07087599B2

関連ノート

読み込み中…