Methanol → HCID 53747526, compound

HRID 1418533Notes

Reaction equation

HRID 1418533 reaction equation
O([C:9]1[CH:14]=[C:13]([O:15][CH3:16])[C:12]([CH2:17][CH2:18][CH3:19])=[CH:11][C:10]=1[F:20])S(C(F)(F)F)(=O)=O.C(N(CC)CC)C.[CH3:28][OH:29].CN([CH:33]=[O:34])C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:20][C:10]1[CH:11]=[C:12]([CH2:17][CH2:18][CH3:19])[C:13]([O:15][CH3:16])=[CH:14][C:9]=1[C:28]([O:34][CH3:33])=[O:29]

Participants

7

Reactant 4

HCID 887MethanolHCID 6228DimethylformamideHCID 8471TriethylamineHCID 53929149HCID 53929149, compound

Product 1

HCID 53747526HCID 53747526, compound

Reagents, catalysts & solvents 2

HCID 812191,3-Bis(diphenylphosphino)propaneCatalystHCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
70 °C

Procedure

2-Fluoro-5-methoxy-4-propylphenyl triflate (3.00 g, 9.5 mmol), triethylamine (2.91 mL, 20.9 mmol) and methanol (7.0 mL, 173 mmol) were dissolved in DMF (30 mL) and the solution was flushed with CO. 1,3-Bis(diphenylphosphino)propane (151 mg, 0.37 mmol) and palladium-acetate (84 mg, 0.37 mmol) were added and the reaction was stirred at 70° C. and atmospheric pressure for 4.5 h. Evaporation of the solvent and co-evaporation with xylene gave a residue which was extracted between Et2O and 2M NaOH and the organic phase was washed brine, dryed over MgSO4 and evaporated to give 2.3 g of crude product. Purification by flash chromatography (SiO2, CH2Cl2 -hexane 1:2) gave methyl 2-fluoro-5-methoxy-4-propylbenzoate (1.46 g) as an oil. 1H NMR (DMSO-d6): δ 7.28 (d, J=6.0 Hz, 1 H), 7.12 (d, J=11.4 Hz, 1 H), 3.83 (s, 3 H), 3.80 (s, 3 H), 2.54 (t, J=7.6 Hz, 2 H), 1.53 (m, J=7.6 Hz, 2 H), 0.87 (t, J=7.4 Hz, 3 H). 13C NMR (DMSO-d6): δ 164.01 (d, J=4 Hz), 155.21 (d, J=251 Hz), 152.95, 138.30 (d, J=8 Hz), 117.93 (d, J=24 Hz), 115.26 (d, J=11 Hz), 111.75, 55.88, 52.20, 31.32, 21.83, 13.66. MS (EI, 70 eV): m/z (rel.int) 226 (M+, 100).

Workup

  1. customthe solution was flushed with CO
  2. customEvaporation of the solvent and co-evaporation with xylene
  3. customgave a residue which
  4. extractionwas extracted between Et2O and 2M NaOH
  5. washthe organic phase was washed brine
  6. customevaporated
  7. customto give 2.3 g of crude product
  8. customPurification by flash chromatography (SiO2, CH2Cl2 -hexane 1:2)

Sources & evidence

ORD record
ord-4e75fb1be9f740bb910155657343a866
Source dataset
uspto-grants-1999_03
Patent number
US05883129

Reaction notes

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