Water → Diethyl (3,5-dimethyl-4-bromophenoxy)methylphosphonate

HRID 2108670Notes

Reaction equation

HRID 2108670 reaction equation
[H-].[Na+].[CH3:3][C:4]1[CH:5]=[C:6]([OH:12])[CH:7]=[C:8]([CH3:11])[C:9]=1[Br:10].S(O[CH2:24][P:25](=[O:32])([O:29][CH2:30][CH3:31])[O:26][CH2:27][CH3:28])(C1C=CC(C)=CC=1)(=O)=O.O>CN(C=O)C>[CH3:3][C:4]1[CH:5]=[C:6]([CH:7]=[C:8]([CH3:11])[C:9]=1[Br:10])[O:12][CH2:24][P:25](=[O:32])([O:29][CH2:30][CH3:31])[O:26][CH2:27][CH3:28]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 819704-Bromo-3,5-dimethylphenolHCID 4193599Diethyl P-[[[(4-methylphenyl)sulfonyl]oxy]methyl]phosphonate

Product 1

HCID 86603470Diethyl (3,5-dimethyl-4-bromophenoxy)methylphosphonate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

To a stirred suspension of NaH (0.5 g, 22.0 mmol) in anhydrous DMF (20 mL) at 0° C. was added 3,5-dimethyl-4-bromophenol (2.2 g, 11.0 mmol) in DMF (5 mL) followed by diethyl tosyloxymethylphosphonate (3.9 g, 24.2 mmol) in DMF (5.0 mL) 30 min later. The reaction mixture was stirred for 14 h at room temperature and poured into water (30 mL). The aqueous solution was extracted with ethyl acetate (2×100 mL) and the combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel, eluting with ethyl acetate-hexanes (2:3) to afford diethyl (3,5-dimethyl-4-bromophenoxy)methylphosphonate as a syrup. (1.85 g, 48%): 1H NMR (300 MHz, CDCl3): δ 6.88 (s, 2H), 4.15-4.25 (m, 6H), 2.41 (s, 2H), 1.40 (t, J=6.0 Hz, 6H); LC-MS m/z=351[α]3H20BrO4P+H]+; TLC conditions: Uniplate silica gel, 250 microns; mobile phase=ethyl acetate-hexanes (2:3); Rf=0.3.

Workup

  1. extractionThe aqueous solution was extracted with ethyl acetate (2×100 mL)
  2. washthe combined organic layers were washed with brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product was purified by column chromatography on silica gel
  7. washeluting with ethyl acetate-hexanes (2:3)

Sources & evidence

ORD record
ord-bc66300a1f304eaa83e7af08d09d373f
Source dataset
uspto-grants-2009_04
Patent number
US07514419B2

Reaction notes

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