Epichlorohydrin → (6-Nitro-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methanol

HRID 2102970Notes

Reaction equation

HRID 2102970 reaction equation
[H-].[Na+].[N+:3]([C:6]1[CH:7]=[C:8]([OH:13])[C:9](=[CH:11][CH:12]=1)[OH:10])([O-:5])=[O:4].[CH2:14]([CH:16]1[O:18][CH2:17]1)Cl>CN(C=O)C.O>[N+:3]([C:6]1[CH:12]=[CH:11][C:9]2[O:10][CH:16]([CH2:17][OH:18])[CH2:14][O:13][C:8]=2[CH:7]=1)([O-:5])=[O:4]

Participants

6

Reactant 3

HCID 7835EpichlorohydrinHCID 24758Sodium hydrideHCID 35051094-Nitrocatechol

Product 1

HCID 12736691(6-Nitro-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methanolYield 32.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

1.93 g of 60% sodium hydride was suspended in 90 mL DMF. At 0° C. a solution of 5.15 g of 4-nitrocatechol was added dropwise over 15 min. Subsequently, 3.9 g of epichlorohydrin in 10 mL DMF were added over 15 min. Stirring was continued at room temperature, then at 80° C. overnight. The mixture was diluted with water and extracted three times with ethyl acetate, dried (Na2SO4), filtered and concentrated under vacuum to give a yellow oil. The oil was purified by column chromatography on silica gel using a EtOAc-hexanes (0-100% gradient) to give the product (2.3 g) as a yellow solid.

Workup

  1. customwas continued at room temperature
  2. customat 80° C.
  3. customovernight
  4. extractionextracted three times with ethyl acetate
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customto give a yellow oil
  9. customThe oil was purified by column chromatography on silica gel using a EtOAc-hexanes (0-100% gradient)

Sources & evidence

ORD record
ord-49b83f34de6443b687e9ce352ef414c7
Source dataset
uspto-grants-2009_08
Patent number
US07576099B2

Reaction notes

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