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

HRID 529269ノート

反応式

HRID 529269 の反応式
[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

参加物

5

反応物 4

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

生成物 1

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

反応条件

温度
70 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-14b51a54644d4f5d99bbed3327a59741
出典データセット
uspto-grants-2016_05
特許番号
US09346842B2

反応ノート

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