Potassium Carbonate → (6'-hydroxy-3-oxospiro[isobenzofuran-1(3H), 9'-[9H]xanthen]-3'-yl)oxy-acetic acid methyl ester

HRID 490042Notes

Reaction equation

HRID 490042 reaction equation
Br[CH2:2][C:3]([O:5][CH3:6])=[O:4].C([O:10][C:11](=[O:34])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]1[C:19]2[C:24]([O:25][C:26]3[C:31]=1[CH:30]=[CH:29][C:28](=[O:32])[CH:27]=3)=[CH:23][C:22]([OH:33])=[CH:21][CH:20]=2)C=C.C([O-])([O-])=O.[K+].[K+].C1([SiH3])C=CC=CC=1>CN(C=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:6][O:5][C:3](=[O:4])[CH2:2][O:32][C:28]1[CH:29]=[CH:30][C:31]2[C:18]3([C:13]4[C:12](=[CH:17][CH:16]=[CH:15][CH:14]=4)[C:11](=[O:34])[O:10]3)[C:19]3[C:24]([O:25][C:26]=2[CH:27]=1)=[CH:23][C:22]([OH:33])=[CH:21][CH:20]=3

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 12752PhenylsilaneHCID 60984Methyl bromoacetateHCID 576736762-(6-Hydroxy-3-oxo-3H-xanthen-9-yl)-benzoic acid 2-propenyl ester

Product 1

HCID 57673664(6'-hydroxy-3-oxospiro[isobenzofuran-1(3H), 9'-[9H]xanthen]-3'-yl)oxy-acetic acid methyl esterYield 62%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

Methyl bromoacetate (0.25 mL, 2.65 mmol) was added dropwise to a stirred mixture of 21 (0.33 g, 0.89 mmol) and K2CO3 (0.36 g, 2.65 mmol) in dry DMF (20 mL) under argon. The resulting mixture was stirred for 4 h at 90° C. The mixture was concentrated, diluted with ethyl acetate, washed with 10% NaHCO3, brine, dried with anhydrous Na2SO4, and evaporated. The residue was dissolved in dry DCM (25 mL). Tetrakis(triphenylphosphine) palladium(0) (58 mg, 0.05 mmol) and phenylsilane (1.1 mL, 8.90 mmol) were added. The mixture was stirred for 2 h at room temperature and concentrated. The residue was purified by column chromatography (ethyl acetate/hexane=1:1) to give 22 as a yellow solid (0.22 g, 62%). TLC (ethyl acetate/hexane, 3:1): Rf=0.5. mp 236° C. 1H NMR (CDCl3/CD3OD, 500 MHz) δ 3.76 (s, 3H, CO2CH3), 4.69 (s, 2H, CH2), 6.68 (m, 6H), 7.19 (d, J=7.5 Hz, 1H), 7.66 (t, J=7.5 Hz, 1H), 7.71 (t, J=7.5 Hz, 1H), 8.01 (d, J=7.5 Hz, 1H). 13C NMR (CDCl3/CD3OD, 125 MHz) δ 52.33, 65.18, 101.86, 102.77, 109.84, 111.55, 112.37, 112.52, 124.05, 124.87, 126.67, 129.00, 129.24, 129.80, 135.21, 152.47, 152.56, 152.94, 159.34, 169.21, 170.15, 171.36, 172.03. ESIMS calcd for C23H17O7 [M+H]+ 405.1. Found 405.2.

Workup

  1. concentrationThe mixture was concentrated
  2. additiondiluted with ethyl acetate
  3. washwashed with 10% NaHCO3, brine
  4. dry with materialdried with anhydrous Na2SO4
  5. customevaporated
  6. dissolutionThe residue was dissolved in dry DCM (25 mL)
  7. stirringThe mixture was stirred for 2 h at room temperature
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography (ethyl acetate/hexane=1:1)

Sources & evidence

ORD record
ord-b6acc544959042bb8b7325ba902fd268
Source dataset
uspto-grants-2009_05
Patent number
US07527934B2

Reaction notes

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