Methanol → HCID 10848200, compound

HRID 2258559Notes

Reaction equation

HRID 2258559 reaction equation
O([C:9]1[CH:14]=[C:13]([O:15][CH3:16])[C:12]([Cl:17])=[C:11]([CH3:18])[C:10]=1[Cl:19])S(C(F)(F)F)(=O)=O.CCN(CC)CC.C[OH:28].O1C[CH2:33][O:32][CH2:31]C1>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>[Cl:19][C:10]1[C:11]([CH3:18])=[C:12]([Cl:17])[C:13]([O:15][CH3:16])=[CH:14][C:9]=1[C:33]([O:32][CH3:31])=[O:28]

Participants

7

Reactant 4

HCID 887MethanolHCID 8471TriethylamineHCID 312751,4-DioxaneHCID 10664790HCID 10664790, compound

Product 1

HCID 10848200HCID 10848200, compound

Reagents, catalysts & solvents 2

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

Procedure

2,4-Dichloro-5-methoxy-3-methylphenyl triflate (7.60 g, 22.4 mmol) was dissolved in dioxan (75 mL), 1,3-bis (diphenylphosphino)propane (371 mg, 0.90 mmol) and palladium acetate (202 mg, 0.90 mmol) were added. After flushing with CO, Et3N (6.90 mL, 49.4 mmol) and MeOH (23 mL) were added. Reaction with CO at 70° C. and at atmospheric pressure for 25° C., filtration and evaporation, of the solvent partition of the residue between Et2O (350 mL) and 3M NH3 (150 mL), extraction of the aqueous layer with Et2O (2×150 mL) followed by washing the combined organic phase with brine (150 mL), drying (MgSO4), evaporation of the solvent gave a crude product. Filtration through SiO2 using EtOAc as the eluent gave 5.2 g of a product which was purified by flash column chromatograhy (SiO2, EtOAc-Hexane 1:3) to yield 4.18 g of the title compound. Mp: 74° C.; 1H NMR(DMSO-d6): δ 7.33 (s, 1H), 3.88 (s, 3H), 3.86 (s, 3H), 2.45 (s, 3H); 13C NMR (DMSO-d6) : δ 165.69, 153.26, 136.09, 130.46, 125.22, 122.95, 110.78, 56.64, 52.72, 17.86; MS (EI, 70 eV): m/z (rel.int.) 250/248 (M+, 53/80), 219/217 (66/100), 191/189 (8/12).

Workup

  1. additionwere added
  2. customReaction with CO at 70° C.
  3. filtrationat atmospheric pressure for 25° C., filtration and evaporation
  4. customof the solvent partition of the residue between Et2O (350 mL) and 3M NH3 (150 mL), extraction of the aqueous layer with Et2O (2×150 mL)
  5. washby washing the combined organic phase with brine (150 mL)
  6. customdrying
  7. custom(MgSO4), evaporation of the solvent
  8. customgave a crude product
  9. filtrationFiltration through SiO2

Sources & evidence

ORD record
ord-91216a76dfaa4f6e9b37887b70352754
Source dataset
uspto-grants-1997_08
Patent number
US05661183

Reaction notes

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