2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 2-t-Butyldimethylsilyl-3-(3,4,5-trimethoxybenzoyl)-6-methoxy-benzofuran

HRID 218822

Reaktionsgleichung

Reaktionsgleichung von HRID 218822
[CH3:1][O:2][C:3]1[CH:4]=[C:5](I)[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].C([Li])CCC.[Si:19]([C:26]1[O:27][C:28]2[CH:36]=[C:35]([O:37][CH3:38])[CH:34]=[CH:33][C:29]=2[C:30]=1[CH:31]=[O:32])([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCCC1.C1(C)C=CC=CC=1>[Si:19]([C:26]1[O:27][C:28]2[CH:36]=[C:35]([O:37][CH3:38])[CH:34]=[CH:33][C:29]=2[C:30]=1[C:31](=[O:32])[C:5]1[CH:4]=[C:3]([O:2][CH3:1])[C:8]([O:9][CH3:10])=[C:7]([O:11][CH3:12])[CH:6]=1)([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:20])[CH3:21]

Komponenten

7

Edukt 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 2981335-Iodo-1,2,3-trimethoxybenzeneHCID 574219572-t-Butyldimethylsilyl-3-formyl-6-methoxybenzofuranHCID 178418339Butyllithium

Produkt 1

HCID 247872412-t-Butyldimethylsilyl-3-(3,4,5-trimethoxybenzoyl)-6-methoxy-benzofuran

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1140TolueneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a stirred solution of 3,4,5-trimethoxyiodobenzene (377 mg, 1.27 mmol) in dry tetrahydrofuran (1 mL) at −78° C. under nitrogen was added n-butyllithium (795 μL, 1.59 mmol, 2M solution in cyclohexane) and the reaction mixture was stirred at this temperature for 40 minutes. After this time a solution of 2-t-butyldimethylsilyl-3-formyl-6-methoxybenzofuran (310 mg, 1.07 mmol) in dry tetrahydrofuran (1 mL) was added to the reaction dropwise via syringe pipette. The reaction mixture was stirred at −60° C. for 20 minutes and then allowed to warm to 0° C., stirred for 10 minutes, quenched with saturated ammonium chloride solution (2 mL) and diluted with ethyl acetate (20 mL). The organic layer was washed with water (10 mL), dried over magnesium sulfate and the solvent was removed under vacuum to give a residue that was co-distilled with toluene. The crude product (908 mg) was dissolved in dry tetrahydrofuran (10 mL) and treated with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (900 mg, 1.59 mmol) was added. The reaction mixture was stirred at room temperature for 16 hours (monitored by tlc) and then loaded onto silica (10 g) and purified by flash chromatography (silica gel, eluent=hexane/diethyl ether/triethylamine, 90:9:1) to afford the title compound as a light yellow paste that crystallised on standing (232 mg, 48%); 1H NMR (300 MHz, CDCl3) δ 7.14(s, 2H, benzoyl Hs), 7.05(d, 1H, J=2.45 Hz), 6.77(dd, 1H, J=8.76, 2.17 Hz), 6.56(d, 1H, J=8.38 Hz), 3.94(s, 3H, OMe), 3.85(s, 6H, 2×OMe), 3.78(s, 3H, OMe), 1.00(s, 9H), 0.28(s, 6H); 13C NMR (75 MHz, CDCl3) δ 190.51(CO), 164.77, 158.23, 158.12, 152.64, 142.35, 133.19, 131.37, 123.19, 121.04, 119.63, 112.26, 107.03, 104.96, 95.00, 60.47, 55.81, 55.60, 55.13, 26.43, 17.29, −6.09.

Aufarbeitung

  1. stirringThe reaction mixture was stirred at −60° C. for 20 minutes
  2. stirringstirred for 10 minutes
  3. customquenched with saturated ammonium chloride solution (2 mL)
  4. additiondiluted with ethyl acetate (20 mL)
  5. washThe organic layer was washed with water (10 mL)
  6. dry with materialdried over magnesium sulfate
  7. customthe solvent was removed under vacuum
  8. customto give a residue that
  9. additionwas added
  10. stirringThe reaction mixture was stirred at room temperature for 16 hours (monitored by tlc)
  11. custompurified by flash chromatography (silica gel, eluent=hexane/diethyl ether/triethylamine, 90:9:1)

Quellen und Nachweise

ORD-Eintrag
ord-ef97f798abdd4b5e9a065f6a3dce727f
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08198466B2

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