Methanol → Ethyl 2-[4-(4-hydroxy-6-oxo-5-phenethylsulfanyl-pyran-2-yl)phenoxy]acetate

HRID 2394014Notes

Reaction equation

HRID 2394014 reaction equation
CO.[OH:3][C:4]1[CH:9]=[C:8]([C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)[O:7][C:6](=[O:17])[C:5]=1[S:18][CH2:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:34][CH2:35][O:36][C:37](=[O:39])[CH3:38]>CN(C)C=O>[CH2:35]([O:36][C:37](=[O:39])[CH2:38][O:16][C:13]1[CH:12]=[CH:11][C:10]([C:8]2[O:7][C:6](=[O:17])[C:5]([S:18][CH2:19][CH2:20][C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)=[C:4]([OH:3])[CH:9]=2)=[CH:15][CH:14]=1)[CH3:34]

Participants

6

Reactant 4

HCID 887MethanolHCID 10796Cesium carbonateHCID 135641-Acetoxy-2-bromoethaneHCID 546812234-hydroxy-6-(4-hydroxyphenyl)-3-[(2-phenylethyl)sulfanyl]-2H-pyran-2-one

Product 1

HCID 54691096Ethyl 2-[4-(4-hydroxy-6-oxo-5-phenethylsulfanyl-pyran-2-yl)phenoxy]acetate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a methanol solution (3 ml) of the 4-hydroxy-6-(4-hydroxyphenyl)-3-[(2-phenylethyl)thio]-2H-pyran-2-one (0.500 g, 1.47 mmol) was added cesium carbonate (0.955 g, 2.94 mmol). The reaction was stirred for 3 hrs. and is then concentrated in vacuo. Next, dimethylformamide (15 mL) is added and the residue is reconcentrated in vacuo to dryness. The solid is then diluted with dimethylformamide (3 mL) and bromoethylacetate (0.491 mL, 2.94 mmol) is added. The slurry is then stirred for 3 hrs. The reaction is quenched by dilution with ethyl acetate (100 mL). The organic layer is washed in succession with; 1N HCl, water, saturated sodium chloride; dried over anhydrous magnesium sulfate. After evaporation of the solvents in vacuo, the crude product was purified by flash column chromatography (SiO2 --230 to 400 mesh) using a gradient of 15% ethyl acetate/hexanes to 50% ethyl acetate/hexanes to 30% ethyl acetate/30% hexanes/40% methylene chloride.: m.p. 169°-171° C.; 1H NMR (400 MHz, DMSO-d6) δ 1.20 (t, 3 H), 2.75 (t, 2 H), 2.96 (t, 2 H), 4.16 (q, 2 H), 4.87 (s, 2 H), 6.69 (s, 1 H), 7.06 (d, 2 H), 7.19 (m, 5 H), 7.73 (d, 2 H), 11.85 (bs, 1 H).

Workup

  1. concentrationand is then concentrated in vacuo
  2. additionNext, dimethylformamide (15 mL) is added
  3. additionis added
  4. stirringThe slurry is then stirred for 3 hrs
  5. customThe reaction is quenched by dilution with ethyl acetate (100 mL)
  6. washThe organic layer is washed in succession with
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customAfter evaporation of the solvents in vacuo
  9. customthe crude product was purified by flash column chromatography (SiO2 --230 to 400 mesh)

Sources & evidence

ORD record
ord-b1fe00dd65c44dfaa39f6bb02df80a56
Source dataset
uspto-grants-1998_09
Patent number
US05808062

Reaction notes

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