Cesium fluoride → Methyl 3,5-bis(methoxymethoxy)-4-(2-methylallyl)benzoate

HRID 1643540Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1643540
[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([O:10][CH2:11][O:12][CH3:13])[C:7](Br)=[C:6]([O:15][CH2:16][O:17][CH3:18])[CH:5]=1.[F-].[Cs+].[CH3:22][C:23](=[CH2:38])[CH2:24][Sn](CCCC)(CCCC)CCCC>CN(C=O)C.[Cu]I.Cl[Pd]Cl.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C>[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([O:10][CH2:11][O:12][CH3:13])[C:7]([CH2:24][C:23]([CH3:38])=[CH2:22])=[C:6]([O:15][CH2:16][O:17][CH3:18])[CH:5]=1

Komponenten

8

Edukt 3

HCID 25953Cesium fluorideHCID 11013379Methallyltri-n-butyltinHCID 59560261Methyl 4-bromo-3,5-bis(methoxymethoxy)benzoate

Produkt 1

HCID 59560052Methyl 3,5-bis(methoxymethoxy)-4-(2-methylallyl)benzoateAusbeute 125,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24290Palladium ChlorideKatalysatorHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 83681Tris(1,1-dimethylethyl)phosphineKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
45 °C

Versuchsvorschrift

To a solution of 4-bromo-3,5-bis-methoxymethoxy-benzoic acid methyl ester (3 h) (3.10 g, 9.25 mmol) in DMF (20 mL) was added CsF (2.80 g, 18.4 mmol), CuI (200 mg, 1.05 mmol), PdCl2 (200 mg, 1.12 mmol), 2-methylallyltributyltin (3.80, 11.0 mmol) and PtBu3 (220 mg, 1.09 mmol). The reaction mixture was degassed and heated to 45° C. overnight. The mixture was filtered through Celite, quenched with H2O (100 mL), extracted with EtOAc (2×100 mL). The organic layers were dried over MgSO4 and concentrated. The residue was purified by flash column chromatography eluting with 5% EtOAc in hexanes to give the desired product as brown oil (3.6 g) which contained tin impurities. 1H NMR (400 MHz, CDCl3) δ 7.44-7.46 (m, 2 H) 5.22 (s, 4 H) 4.61-4.76 (m, 1 H) 4.38-4.55 (m, 1 H) 3.90 (s, 3 H) 3.47 (s, 6 H) 3.42-3.45 (m, 2 H) 1.80 (s, 3 H); LCMS for C16H22O6 m/z 311.10 (M+H)+.

Aufarbeitung

  1. customThe reaction mixture was degassed
  2. filtrationThe mixture was filtered through Celite
  3. customquenched with H2O (100 mL)
  4. extractionextracted with EtOAc (2×100 mL)
  5. dry with materialThe organic layers were dried over MgSO4
  6. concentrationconcentrated
  7. customThe residue was purified by flash column chromatography
  8. washeluting with 5% EtOAc in hexanes

Quellen und Nachweise

ORD-Eintrag
ord-b648139b108f4e518df8e479b66ff052
Quelldatensatz
uspto-grants-2012_02
Patentnummer
US08119624B2

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