Ethyl Acetate → Methyl 6-(benzenesulfonylmethyl)-2-hydroxy-3-(2-vinylfuran-3-yl)-benzoate

HRID 1778351Notes

Reaction equation

HRID 1778351 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[K+].[C:11]1([S:17]([CH2:20][C:21]2[C:26]([C:27]([O:29][CH3:30])=[O:28])=[C:25]([OH:31])[C:24]([C:32]3[CH:36]=[CH:35][O:34][C:33]=3[CH:37]=O)=[CH:23][CH:22]=2)(=[O:19])=[O:18])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[C:39](OCC)(=O)C.[Cl-].[NH4+]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:11]1([S:17]([CH2:20][C:21]2[C:26]([C:27]([O:29][CH3:30])=[O:28])=[C:25]([OH:31])[C:24]([C:32]3[CH:36]=[CH:35][O:34][C:33]=3[CH:37]=[CH2:39])=[CH:23][CH:22]=2)(=[O:19])=[O:18])[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 3251421Potassium bis(trimethylsilyl)amideHCID 86684730Methyl 6-(benzenesulfonylmethyl)-3-(2-formylfuran-3-yl)-2-hydroxybenzoate2×

Product 1

HCID 66685753Methyl 6-(benzenesulfonylmethyl)-2-hydroxy-3-(2-vinylfuran-3-yl)-benzoate

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

A suspension of methyltriphenylphosphonium bromide (pre-dried under vacuum at 60° C., 3.80 g) in THF (60 mL) was cooled to 5° C., under nitrogen. Potassium bis-(trimethylsilyl)amide (0.5M in toluene, 21.3 mL) was added and the suspension was warmed to room temperature and stirred for 45 minutes. It was cooled to −78° C. and a solution of methyl 6-(benzenesulfonylmethyl)-3-(2-formylfuran-3-yl)-2-hydroxybenzoate (Intermediate 28, 1.42 g) in THF (40 mL) was added and the mixture was warmed to room temperature and stirred for 2.5 hours. Ethyl acetate and a saturated aqueous solution of ammonium chloride were added to the mixture and the organic layer was separated, washed with brine, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 15-35% to give methyl 6-(benzenesulfonylmethyl)-2-hydroxy-3-(2-vinylfuran-3-yl)-benzoate (1.24 g) as a white solid.

Workup

  1. temperaturethe suspension was warmed to room temperature
  2. temperatureIt was cooled to −78° C.
  3. temperaturethe mixture was warmed to room temperature
  4. stirringstirred for 2.5 hours
  5. customthe organic layer was separated
  6. washwashed with brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customThe filtrate was evaporated to dryness
  10. customthe residue was purified by chromatography on silica
  11. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 15-35%

Sources & evidence

ORD record
ord-b6507285499f4280a0aa9ff34b0cf0e3
Source dataset
uspto-grants-2016_02
Patent number
US09266896B2

Reaction notes

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