Dimethylformamide → Dimethyl [2-(4-fluoro-2-nitrophenyl)-1-phenylethyl]malonate

HRID 2267607

反応式

HRID 2267607 の反応式
C1(=O)O[CH:6](C2C=CC=CC=2)[O:5][C:3](=[O:4])C1.[H-].[Na+].[F:17][C:18]1[CH:23]=[CH:22][C:21]([CH3:24])=[C:20]([N+:25]([O-:27])=[O:26])[CH:19]=1.[CH3:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33].[C:34]([O:37][CH2:38]C)(=[O:36])[CH3:35].[CH3:40]N(C=O)C>>[CH3:6][O:5][C:3](=[O:4])[CH:35]([CH:40]([C:30]1[CH:29]=[CH:28][CH:33]=[CH:32][CH:31]=1)[CH2:24][C:21]1[CH:22]=[CH:23][C:18]([F:17])=[CH:19][C:20]=1[N+:25]([O-:27])=[O:26])[C:34]([O:37][CH3:38])=[O:36]

参加物

6

反応物 5

HCID 6228Dimethylformamide2 回HCID 24758Sodium hydrideHCID 679654-Fluoro-2-nitrotolueneHCID 9338292-Phenyl-1,3-dioxane-4,6-dioneHCID 21226206Ethyl acetate hexane2 回

生成物 1

HCID 59688514Dimethyl [2-(4-fluoro-2-nitrophenyl)-1-phenylethyl]malonate収率 30%

実験手順

A solution of benzylidene malonate (14.2 g) in DMF (280 mL) was treated with sodium hydride (2.57 g, 95%). A solution of 4-fluoro-2-nitrotoluene in DMF (10 mL) was added over 1H, and the reaction mixture was stirred at RT overnight and then quenched by the addition of glacial acetic acid (175 mL) at 0° C. A total of 500 mL of 70:30 water-methanol was added with stirring, and the organics were extracted with ethyl acetate. The organic extracts were combined and washed with saturated aqueous potassium carbonate solution (2×) and brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give a dark brown oil. Flash chromatography on silica gel (75:25 hexane-ethyl acetate, then 50:50 hexane-ethyl acetate) provided 7.0 g (30%) of the title compound as a red-brown solid. 1H NMR (300 MHz, CDCl3) δ 3.72 (d, 2H), 3.73 (d, 1H), 4.32 (m, 1H), 7.09-7.29 (m, 7H), 7.71 (m, 1H). MS APCI, m/z=398 (M+Na). LC/MS: 2.66 min.

後処理

  1. customquenched by the addition of glacial acetic acid (175 mL) at 0° C
  2. additionA total of 500 mL of 70:30 water-methanol was added
  3. stirringwith stirring
  4. extractionthe organics were extracted with ethyl acetate
  5. washwashed with saturated aqueous potassium carbonate solution (2×) and brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give a dark brown oil

出典と根拠

ORDレコード
ord-d1c05d2a8f4d47f5ba7021ba682c1f15
出典データセット
uspto-grants-2010_12
特許番号
US07858776B2

関連ノート

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