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

HRID 993315ノート

反応式

HRID 993315 の反応式
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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-3d93479d1d0a4e2b97b948e6be3e2501
出典データセット
uspto-grants-2002_10
特許番号
US06472416B1

反応ノート

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