Water → Bis(1,3-benzodioxol-5-yl)methanol

HRID 2258023Notes

Reaction equation

HRID 2258023 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]2[O:8][CH2:9][O:10][C:4]=2[CH:3]=1.C([Li])CCC.[CH:16]1[C:21]([CH:22]=[O:23])=[CH:20][C:19]2[O:24][CH2:25][O:26][C:18]=2[CH:17]=1.O>O1CCCC1>[O:8]1[C:5]2[CH:6]=[CH:7][C:2]([CH:22]([C:21]3[CH:16]=[CH:17][C:18]4[O:26][CH2:25][O:24][C:19]=4[CH:20]=3)[OH:23])=[CH:3][C:4]=2[O:10][CH2:9]1

Participants

6

Reactant 4

HCID 962WaterHCID 8438PiperonalHCID 758311-Bromo-3,4-(methylenedioxy)benzeneHCID 178418339Butyllithium

Product 1

HCID 384225Bis(1,3-benzodioxol-5-yl)methanolYield 933.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 4-bromo-1,2-(methylenedioxy)benzene (5.02 g, 2.5 mmol) in 100 mL of dry tetrahydrofuran is cooled to -78° C. n-Butyllithium (15.6 mL, 2.5 mmol) is added dropwise to the reaction. The white suspension is stirred for another hour. Piperonal (4.12 g, 2.4 mmol) in 20 mL of tetrahydrofuran is added. The reaction is warmed to room temperature and stirred overnight. Water (50 mL) is added to quench the reaction. Layers are separated and the aqueous phase is extracted with 3×40 mL of ethyl acetate. The combined organics are dried (magnesium sulfate) and filtered. Solvent is removed in vacuo and the residue is purified by silica gel chromatography eluting with 20% ethyl acetate-hexane to give 6.1 g (90%) of product as a white solid;

Workup

  1. additionis added dropwise to the reaction
  2. stirringstirred overnight
  3. customto quench
  4. customthe reaction
  5. customLayers are separated
  6. extractionthe aqueous phase is extracted with 3×40 mL of ethyl acetate
  7. dry with materialThe combined organics are dried (magnesium sulfate)
  8. filtrationfiltered
  9. customSolvent is removed in vacuo
  10. customthe residue is purified by silica gel chromatography
  11. washeluting with 20% ethyl acetate-hexane

Sources & evidence

ORD record
ord-5fb024214a264e17af322502a5cc24a6
Source dataset
uspto-grants-1997_08
Patent number
US05658943

Reaction notes

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