Tetrahydrofuran → 2-Methyl-3-(3,4,5-trimethoxybenzoyl)-6-methoxy-7-isopropoxy-benzo[b]furan

HRID 1192015Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1192015
[CH:1]([O:4][C:5]1[C:10]([O:11][CH3:12])=[CH:9][CH:8]=[C:7](I)[C:6]=1[OH:14])([CH3:3])[CH3:2].C([Mg]Br)#CC.[CH3:20][O:21][C:22]1[CH:23]=[C:24](I)[CH:25]=[C:26]([O:30][CH3:31])[C:27]=1[O:28][CH3:29].[O:33]1[CH2:37][CH2:36][CH2:35][CH2:34]1>>[CH3:37][C:36]1[O:14][C:6]2[C:5]([O:4][CH:1]([CH3:3])[CH3:2])=[C:10]([O:11][CH3:12])[CH:9]=[CH:8][C:7]=2[C:35]=1[C:34](=[O:33])[C:24]1[CH:23]=[C:22]([O:21][CH3:20])[C:27]([O:28][CH3:29])=[C:26]([O:30][CH3:31])[CH:25]=1

Komponenten

5

Edukt 4

HCID 8028TetrahydrofuranHCID 2981335-Iodo-1,2,3-trimethoxybenzeneHCID 247864402-Isopropoxy-3-methoxy-6-iodophenolHCID 178419101HCID 178419101, Verbindung

Produkt 1

HCID 601490202-Methyl-3-(3,4,5-trimethoxybenzoyl)-6-methoxy-7-isopropoxy-benzo[b]furan

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

To a stirred solution of 2-isopropoxy-3-methoxy-6-iodophenol (308 mg, 1.00 mmol) in dry tetrahydrofuran (2 mL) was added dropwise a solution of 1-propynyl magnesium bromide (5, 6 mL, 3 mmol, 0.5 M solution in THF) at 0° C. under nitrogen. Dichloro-bis-triphenylphosphine palladium catalyst (40 mg, 0.06 mmol) was added and the reaction mixture was heated to 70° C. for 3 hours (tlc). The solvent was removed under vacuum and the residue was dried under vacuum. Dry dimethylsulfoxide (8 mL) was added and the nitrogen atmosphere was replaced with carbon monoxide. 3,4,5-Trimethoxyiodobenzene 6 (310 mg 1.05 mmol) was added and the reaction mixture was stirred at 90° C. for 17 hours and then quenched with saturated ammonium chloride solution and extracted with ethyl acetate (2×25 mL). The organic layer was washed with water and dried over magnesium sulphate. The crude product was purified by flash chromatography (silica gel, eluent=hexane/diethyl ether; 8:2-7:3) to afford the title compound as a creamy white solid. The product was crystallized from methanol. Yield—290 mg, 70%; 1H NMR (300 MHz, CDCl3) δ-7.10 (s, 2H, benzoyl Hs), 7.07 (d, 1H), 6.85 (d, 1H, J=8.57), 4.74-4.68 (m, 1H), 3.93 (s, 3H, OMe), 3.87 (s, 3H, OMe), 3.83 (s, 6H, 2×OMe), 2.52 (s, 3H, Me), 1.37 (d, 6H, J=6.18 Hz).

Aufarbeitung

  1. customThe solvent was removed under vacuum
  2. customthe residue was dried under vacuum
  3. additionDry dimethylsulfoxide (8 mL) was added
  4. customquenched with saturated ammonium chloride solution
  5. extractionextracted with ethyl acetate (2×25 mL)
  6. washThe organic layer was washed with water
  7. dry with materialdried over magnesium sulphate
  8. customThe crude product was purified by flash chromatography (silica gel, eluent=hexane/diethyl ether; 8:2-7:3)

Quellen und Nachweise

ORD-Eintrag
ord-ad864bb97f974dd28bdf15109ef9b8f3
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08680135B2

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