Boron trifluoride etherate → 6'-Bromospiro[cyclohexane-1,2'-indene]-1',4(3'H)-dione

HRID 336565

反応式

HRID 336565 の反応式
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7](=[CH2:12])[C:8]2=[O:11])=[CH:4][CH:3]=1.C[Si](C)(C)[O:15][C:16]([CH:18]=[CH2:19])=[CH2:17].B(F)(F)F.CCOCC>ClCCl>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:19][CH2:18][C:16](=[O:15])[CH2:17][CH2:12]3)[C:8]2=[O:11])=[CH:4][CH:3]=1

参加物

5

反応物 3

HCID 8000Boron trifluoride etherate2 回HCID 5546572-(Trimethylsiloxy)-1,3-butadieneHCID 581971666-bromo-2-methylene-2,3-dihydro-1H-inden-1-one

生成物 1

HCID 581972056'-Bromospiro[cyclohexane-1,2'-indene]-1',4(3'H)-dione収率 48.1%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

In a flame dried 20 mL vial was placed 6-bromo-2-methylene-2,3-dihydro-1H-inden-1-one (98 mg, 0.441 mmol) and it was dissolved in dichloromethane (4.5 mL). To this solution was added 2-trimethylsilyloxy-1,3-butadiene (98 μL, 0.565 mmol) and the solution was cooled down to −78° C. After stirring for 5 minutes, BF3.OEt2 (27 mL, 0.219 mmol) was slowly added. After 5 minutes of the BF3.OEt2 addition, TLC indicated consumption of the dienophile. The reaction was quenched with MeOH (300 μL), allowed to stir for 5 minutes at −78° C. and then warmed up to room temperature. Once at room temperature, 2M HCl (7 mL) was added. The phases were separated and the aqueous phase was back-extracted with dichloromethane twice (5 mL/each). The combined organic phases were dried over MgSO4, filtered and concentrated under reduce pressure. The crude material was purified by flash chromatography (ISCO, 12 g SiO2 cartridge, ethyl acetate/hexanes as the eluents). The corresponding fractions were combined and concentrated under reduce pressure yielding 6′-bromospiro[cyclohexane-1,2′-indene]-1′,4(3′H)-dione (62 mg, 0.212 mmol, 48% yield). 1H NMR=(CDCl3, 400 MHz) δ 7.68 (d, J=2.0 Hz, 1H), 7.51 (dd, J=8.0, 2.0 Hz, 1H), 7.16 (d, J=8.0 Hz, 1H), 2.94 (s, 2H), 2.48 (dt, J=15.2, 5.6 Hz, 2H), 2.22 (ddd, J=15.2, 10.8, 5.6 Hz, 2H), 1.98 (ddd, J=13.6, 11.2, 5.2 Hz, 2H), 1.65 (m, 2H) ppm.

後処理

  1. customIn a flame dried 20 mL
  2. customconsumption of the dienophile
  3. customThe reaction was quenched with MeOH (300 μL)
  4. stirringto stir for 5 minutes at −78° C.
  5. temperaturewarmed up to room temperature
  6. additionOnce at room temperature, 2M HCl (7 mL) was added
  7. customThe phases were separated
  8. extractionthe aqueous phase was back-extracted with dichloromethane twice (5 mL/each)
  9. dry with materialThe combined organic phases were dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude material was purified by flash chromatography (ISCO, 12 g SiO2 cartridge, ethyl acetate/hexanes as the eluents)
  13. concentrationconcentrated

出典と根拠

ORDレコード
ord-46d0665a0cde478b80f834eb41b55795
出典データセット
uspto-grants-2014_11
特許番号
US08889703B2

関連ノート

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