Potassium Carbonate → HCID 11573667, compound

HRID 1356594Notes

Reaction equation

HRID 1356594 reaction equation
Br[CH:2]([CH2:7][CH2:8][CH2:9]Br)[C:3]([O:5][CH3:6])=[O:4].[OH:11][C:12]1[CH:13]=[C:14]([CH:19]=[CH:20][CH:21]=1)[C:15]([O:17][CH3:18])=[O:16].C([O-])([O-])=O.[K+].[K+].[C:28]([O-:31])(=[S:30])[CH3:29].[K+]>CN(C=O)C.CCOC(C)=O>[C:28]([S:30][CH2:9][CH2:8][CH2:7][CH:2]([C:3]([O:5][CH3:6])=[O:4])[O:11][C:12]1[CH:13]=[C:14]([CH:19]=[CH:20][CH:21]=1)[C:15]([O:17][CH3:18])=[O:16])(=[O:31])[CH3:29]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 88068Methyl 3-HydroxybenzoateHCID 10912698Methyl 2,5-dibromopentanoateHCID 23670855Potassium ethanethioate

Product 1

HCID 11573667HCID 11573667, compoundYield 37%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of methyl 2,5-dibromopentanoate XIII (22.00 g, 80.3 mmol) and methyl 3-hydroxybenzoate XIV (10.18 g, 66.9 mmol) in DMF (80 mL) was added K2CO3 (12.94 g, 93.7 mmol) at room temperature. The mixture was stirred at room temperature under N2 for 12 hours, then heated at 70° C. for 1 h. Potassium thioacetate (22.93 g, 200.8 mmol) was added to the mixture, which was heated at 70° C. for 2 hours. The mixture was allowed to cool to room temperature and was diluted with EtOAc (1000 mL). The mixture was washed with H2O (3×300 mL) and brine (2×300 mL). The organic layer was dried over MgSO4, filtered and concentrated. The crude product was purified by flash chromatography (gradient elution: 10% to 20% EtOAc/hexanes) to afford methyl 3-(4-acetylthio-1-methoxycarbonyl-butoxy)-benzoate XV (8.40 g, 24.7 mmol, 37%) as a yellow oil: Rf 0.26 (hexanes/EtOAc, 4:1): 1H NMR (CDCl3) δ 1.73-1.88 (m, 2H), 2.01-2.08 (m, 2H), 2.32 (s, 3H), 2.93 (t, J=7.2 Hz, 2H), 3.75 (s, 3H), 3.89 (s, 3H), 4.69 (t, J=6.2 Hz, 1H), 7.07 (dm, J=8.0 Hz, 1H), 7.33 (t, J=7.9 Hz, 1H), 7.50 (m, 1H), 7.65 (dm, J=7.7 Hz, 1H); 13C NMR (CDCl3) δ 25.3, 28.3, 30.5, 31.4, 52.1, 52.2, 75.8, 115.4, 120.0, 122.8, 129.5, 131.4, 157.5, 166.4, 171.3, 195.4.

Workup

  1. temperatureheated at 70° C. for 1 h
  2. temperaturewas heated at 70° C. for 2 hours
  3. temperatureto cool to room temperature
  4. washThe mixture was washed with H2O (3×300 mL) and brine (2×300 mL)
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified by flash chromatography (gradient elution: 10% to 20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-c4765e372af24643bde59c9a8599fc97
Source dataset
uspto-grants-2003_07
Patent number
US06586623B2

Reaction notes

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