4-(Methylthio)benzoyl chloride → Ethyl 2-(4-fluorophenyl)-3-(4-(methylthio)phenyl)-3-oxopropanoate

HRID 993315Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 993315
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[F:11][C:12]1[CH:17]=[CH:16][C:15]([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:14][CH:13]=1.[CH3:24][S:25][C:26]1[CH:34]=[CH:33][C:29]([C:30](Cl)=[O:31])=[CH:28][CH:27]=1>C1COCC1>[F:11][C:12]1[CH:13]=[CH:14][C:15]([CH:18]([C:30]([C:29]2[CH:33]=[CH:34][C:26]([S:25][CH3:24])=[CH:27][CH:28]=2)=[O:31])[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:16][CH:17]=1

Komponenten

5

Edukt 3

HCID 740424-(Methylthio)benzoyl chlorideHCID 2733832Lithium HexamethyldisilazideHCID 3013910Benzeneacetic acid, 4-fluoro-, ethyl ester

Produkt 1

HCID 11256029Ethyl 2-(4-fluorophenyl)-3-(4-(methylthio)phenyl)-3-oxopropanoateAusbeute 69 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

1 N Lithium bis(trimethylsilyl)amide (20 mL, 20 mmol) was added dropwise to a solution of ethyl (4-fluorophenyl)acetate prepared according to the method of Example 1A, (3.84 g, 20 mmol) in THF (20 mL) at −78° C. After 15 minutes the mixture was treated dropwise with a suspension of crude 4-(methylthio)benzoyl chloride (3.7 g, 20 mmol) in THF (50 mL), and the resulting mixture was stirred at −78° C. for 60 minutes. The reaction was quenched with saturated NH4Cl and extracted with ethyl acetate. The acetate layer was washed with water, brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was chromatographed (silica gel, 19:1 CH2Cl2-ethyl acetate) to provide the desired product (yield: 4.55 g; 69%). MS (DCI-NH3) m/z 333 (M+H)+, 350 (M+NH4)+; 1H NMR (300 MHz, CDCl3) δ1.25 (m, 3H), 2.50 (s, 3H), 4.20 (m, 2H), 5.53 (s, 1H), 7.03 (t, J=9 Hz, 2H), 7.22 (d, J=9 Hz, 2H), 7.38 (m, 2H), 7.85 (d, J=9 Hz, 2H).

Aufarbeitung

  1. customprepared
  2. customThe reaction was quenched with saturated NH4Cl
  3. extractionextracted with ethyl acetate
  4. washThe acetate layer was washed with water, brine
  5. dry with materialdried over anhydrous MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was chromatographed (silica gel, 19:1 CH2Cl2-ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-3d93479d1d0a4e2b97b948e6be3e2501
Quelldatensatz
uspto-grants-2002_10
Patentnummer
US06472416B1

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