1-Bromo-3,4-(methylenedioxy)benzene → 8-(Benzo[d][1,3]dioxol-5-yl)-1,4-dioxaspiro[4.5]decan-8-ol

HRID 1893215Notes

Reaction equation

HRID 1893215 reaction equation
[Li]CCCC.Br[C:7]1[CH:15]=[CH:14][C:10]2[O:11][CH2:12][O:13][C:9]=2[CH:8]=1.[O:16]1[C:20]2([CH2:25][CH2:24][C:23](=[O:26])[CH2:22][CH2:21]2)[O:19][CH2:18][CH2:17]1>C1COCC1>[O:11]1[C:10]2[CH:14]=[CH:15][C:7]([C:23]3([OH:26])[CH2:24][CH2:25][C:20]4([O:19][CH2:18][CH2:17][O:16]4)[CH2:21][CH2:22]3)=[CH:8][C:9]=2[O:13][CH2:12]1

Participants

5

Reactant 3

HCID 758311-Bromo-3,4-(methylenedioxy)benzeneHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 178418339Butyllithium

Product 1

HCID 109128408-(Benzo[d][1,3]dioxol-5-yl)-1,4-dioxaspiro[4.5]decan-8-ol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of n-BuLi (2.5 M in hexanes, 24 mL, 60 mmol) was dropped slowly into a solution of 5-bromo-benzo[1,3]dioxole (Aldrich, 10.0 g, 50 mmol) in THF (100 mL) at −78° C. over 10 min. The reaction was stirred for additional 20 min. at −78° C. A solution of 1,4-dioxa-spiro[4.5]decan-8-one (Aldrich, 8.60 g, 55 mmol) in THF (20 mL) was slowly dropped into the reaction. After addition, the reaction was stirred for additional 2 hours at −78° C. The reaction was then quenched with diluted NH4Cl solution and warmed to room temperature. The solvent was removed in vacuo and the residue was partitioned between ethyl acetate and water. The organic layer was washed with brine, dried over anhydrous Na2SO4, filtered and concentrated to give a yellow solid, which was then purified by silica gel column on a CombiFlash® system (Teledyne Isco, Inc, Lincoln, Nebr.) using hexanes and ethyl acetate (from 10% ethyl acetate to 100% ethyl acetate) to afford the title compound as a white solid.

Workup

  1. additionAfter addition
  2. stirringthe reaction was stirred for additional 2 hours at −78° C
  3. customThe reaction was then quenched with diluted NH4Cl solution
  4. temperaturewarmed to room temperature
  5. customThe solvent was removed in vacuo
  6. customthe residue was partitioned between ethyl acetate and water
  7. washThe organic layer was washed with brine
  8. dry with materialdried over anhydrous Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto give a yellow solid, which
  12. customwas then purified by silica gel column on a CombiFlash® system (Teledyne Isco, Inc, Lincoln, Nebr.)

Sources & evidence

ORD record
ord-c94530aa371a4256b6e4beff1b1dc41d
Source dataset
uspto-grants-2013_08
Patent number
US08513229B2

Reaction notes

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