Methanol → 7-bromo-4-fluoro-2-methoxy-9-(2-methoxyethylidene)-9H-xanthene

HRID 335978Notes

Reaction equation

HRID 335978 reaction equation
[Br:1][C:2]1[CH:15]=[C:14]2[C:5]([O:6][C:7]3[C:8]([F:21])=[CH:9][C:10]([O:19][CH3:20])=[CH:11][C:12]=3[C:13]2([CH:17]=[CH2:18])O)=[CH:4][CH:3]=1.[CH3:22][OH:23].S(=O)(=O)(O)O>>[Br:1][C:2]1[CH:15]=[C:14]2[C:5]([O:6][C:7]3[C:8]([F:21])=[CH:9][C:10]([O:19][CH3:20])=[CH:11][C:12]=3[C:13]2=[CH:17][CH2:18][O:23][CH3:22])=[CH:4][CH:3]=1

Participants

4

Reactant 3

HCID 887MethanolHCID 1118Sulfuric AcidHCID 673829547-bromo-4-fluoro-2-methoxy-9-vinyl-9H-xanthen-9-ol

Product 1

HCID 673832827-bromo-4-fluoro-2-methoxy-9-(2-methoxyethylidene)-9H-xantheneYield 42.8%

Conditions

Temperature
55 °C

Procedure

To a 250 mL of RBF were added 7-bromo-4-fluoro-2-methoxy-9-vinyl-9H-xanthen-9-ol (8.69 g, 24.75 mmol), methanol (100 mL, 2475 mmol) and sulfuric acid (0.2M in water) (12.4 mL, 2.48 mmol). The mixture was heated to 55° C. for 25 min. The solvent was removed and the residue was diluted with EtOAc. The organic layer was washed by saturated aqueous NaHCO3. The aqueous layer was further extracted with EtOAc. The organic layers were combined and washed with brine, dried over magnesium sulfate, filtered and concentrated in vacuo to give the crude material as an oil. The crude product was purified by 35% to 50% to 75% to 100% DCM in Heptane to yield 7-bromo-4-fluoro-2-methoxy-9-(2-methoxyethylidene)-9H-xanthene (3.87 g, 10.60 mmol).

Workup

  1. customThe solvent was removed
  2. additionthe residue was diluted with EtOAc
  3. washThe organic layer was washed by saturated aqueous NaHCO3
  4. extractionThe aqueous layer was further extracted with EtOAc
  5. washwashed with brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give the crude material as an oil
  10. customThe crude product was purified by 35% to 50% to 75% to 100% DCM in Heptane

Sources & evidence

ORD record
ord-ef58c94cfe574500889b4c09d4b548a2
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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