Thiazole → Methyl 4-(thiazol-2-Yl)benzoate

HRID 348889

Reaktionsgleichung

Reaktionsgleichung von HRID 348889
[S:1]1[CH:5]=[CH:4][N:3]=[CH:2]1.C([Li])CCC.I[C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=1>O1CCCC1.C(OCC)C.[Cl-].[Zn+2].[Cl-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[S:1]1[CH:5]=[CH:4][N:3]=[C:2]1[C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=1

Komponenten

8

Edukt 3

HCID 9256ThiazoleHCID 69273Methyl 4-iodobenzoateHCID 178418339Butyllithium

Produkt 1

HCID 11241445Methyl 4-(thiazol-2-Yl)benzoate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 3007855ZincchlorideKatalysatorHCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a −70° C., stirred solution of thiazole (270 μL, 3.8 mmol) in tetrahydrofuran (10 mL) is added n-butyl lithium (2.6 mL of a 1.6 M solution in hexanes, 4.2 mmol). After 30 min, zinc chloride (11.4 mL of a 1.0 M solution in diethyl ether, 11.4 mmol) is added. The reaction mixture is warmed to 0° C. and methyl 4-iodobenzoate (1 g, 3.8 mmol) and palladium(0) tetrakis(triphenylphosphine) (530 mg, 0.4 mmol) are added. The reaction mixture is heated at 70° C. for 20 h under argon, cooled to room temperature, and then partitioned between ethyl acetate and water. The organic layer is washed with water, and brine, dried (sodium sulfate), filtered, and concentrated under reduced pressure. Purification by flash column chromatography (3:1 hexanes/ethyl acetate) yields the title compound. 1H NMR (300 MHz, CDCl3) δ 8.14–8.03 (m, 4H), 7.93–7.92 (m, 1H), 7.42–7.41 (m, 1H), 3.95 (s, 3H).

Aufarbeitung

  1. temperatureThe reaction mixture is heated at 70° C. for 20 h under argon
  2. temperaturecooled to room temperature
  3. custompartitioned between ethyl acetate and water
  4. washThe organic layer is washed with water, and brine
  5. dry with materialdried (sodium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customPurification by flash column chromatography (3:1 hexanes/ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-2bac21ef6e944361a45ad2faa71ba177
Quelldatensatz
uspto-grants-2007_02
Patentnummer
US07176242B2

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