2,3-Dichloropropene → HCID 18546015, compound

HRID 1267239Notes

Reaction equation

HRID 1267239 reaction equation
[OH:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][C@H:8]([CH2:11][OH:12])[O:7][C:6]=2[CH:13]=1.[H-].[Na+].[Cl:16][C:17]([CH2:19]Cl)=[CH2:18]>CN(C)C=O>[Cl:16][C:17](=[CH2:18])[CH2:19][O:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][CH:8]([CH2:11][OH:12])[O:7][C:6]=2[CH:13]=1

Participants

5

Reactant 3

HCID 65652,3-DichloropropeneHCID 24758Sodium hydrideHCID 20579158HCID 20579158, compound

Product 1

HCID 18546015HCID 18546015, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1.36 g (7.47 mmole) of (2S)-(7-hydroxy-2,3-dihydro-1,4-benzodioxin-2-yl)methanol in 50 mL of N,N-dimethylformamide was added 0.36 g (9.0 mmole) of 60% sodium hydride/mineral oil dispersion and the mixture stirred for 30 minutes at room temperature under nitrogen. Next 1.0 mL (11 mmole) of 2,3-dichloro-1-propene was added and the reaction heated at 60° C. under nitrogen for 40 hours. The solvent was removed in vacuum and replaced with 200 mL of methylene chloride. The solution was washed with 50 mL of 0.1 N aqueous HCl and with water, dried over sodium sulfate, filtered and concentrated in vacuum to ˜2 g of a very dark oil. The oil was column chromatographed on silica gel with 20% hexane/methylene chloride and the product fractions combined and concentrated in vacuum to give 1.1 g of the (S)-enantiomer of the title compound as a pale yellow oil. 1H-NMR (d6-DMSO): doublet 7.76 δ (1H); doublet 6.53 δ (1H); doublet of doublets 6.45 δ (1H); doublet 5.66 δ (1H); doublet 5.48 δ (1H); broad singlet 5.04 δ (1H); singlet 4.6 δ (2H); doublet of doublets 4.25 δ (1H); multiplet 4.12 δ (1H); doublet of doublets 3.92 δ (1H); multiplet 3.6 δ (2H).

Workup

  1. temperaturethe reaction heated at 60° C. under nitrogen for 40 hours
  2. customThe solvent was removed in vacuum
  3. washThe solution was washed with 50 mL of 0.1 N aqueous HCl and with water
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuum to ˜2 g of a very dark oil
  7. customchromatographed on silica gel with 20% hexane/methylene chloride
  8. concentrationconcentrated in vacuum

Sources & evidence

ORD record
ord-303fa607f88148d3ac36475920aa8b67
Source dataset
uspto-grants-2003_04
Patent number
US06552049B2

Reaction notes

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