1-(2,6-Dichlorophenyl)ethan-1-one → HCID 12431705, compound

HRID 860399Notes

Reaction equation

HRID 860399 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH3:11][C:12]([C:14]1[C:19]([Cl:20])=[CH:18][CH:17]=[CH:16][C:15]=1[Cl:21])=[O:13].[N+:22]([C:25]1[CH:26]=[C:27]([CH:32]=[CH:33][CH:34]=1)[C:28]([C:30]#[N:31])=[O:29])([O-:24])=[O:23]>O1CCCC1>[N+:22]([C:25]1[CH:26]=[C:27]([CH:32]=[CH:33][CH:34]=1)[C:28]([C:30]#[N:31])=[O:29])([O-:24])=[O:23].[Cl:21][C:15]1[CH:16]=[CH:17][CH:18]=[C:19]([Cl:20])[C:14]=1[C:12](=[O:13])[CH2:11][C:28]([C:27]1[CH:32]=[CH:33][CH:34]=[C:25]([N+:22]([O-:24])=[O:23])[CH:26]=1)=[O:29]

Participants

6

Reactant 3

HCID 748771-(2,6-Dichlorophenyl)ethan-1-oneHCID 2733832Lithium HexamethyldisilazideHCID 12431705HCID 12431705, compound

Product 2

HCID 12431705HCID 12431705, compoundHCID 85829274HCID 85829274, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

To a stirred solution of lithium bis(trimethylsilyl)amide (1.0 molar in tetrahydrofuran, 11 mL, 1.1 mole equivalent) cooled at −70 under nitrogen was added dropwise a solution of 2,6 dichloroacetophenone (965 mg, 1.0 molar equivalent) in anhydrous tetrahydrofuran. The resulting mixture was stirred at −20° C. for 2 h. The reaction mixture was re-cooled to −70° C., and a solution of 3-nitrobenzoylcyanide (900 mg, 1.0 molar equivalent) in tetrahydrofuran was added dropwise. The 3-nitrobenzoylcyanide was prepared according to the procedures of S. Yamaguchi et. al. in, Bull. Chem. Soc. Jpn. 1989, 62,3036–3037. The mixture was allowed to warm to room temp over 1 h and was stirred at room temperature for 2 h. The reaction was quenched by the addition of saturated aqueous ammonium chloride. The reaction mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to dryness. The crude solid product was purified by column chromatography over silica gel using hexanes and ethyl acetate to give the desired 1-(2,6-dichlorophenyl)-3-(3-nitrophenyl)-1,3 propanedione. NMR 300 MHz (CDCL3) 8.75 (m, 1H), 8.40 (m, 1H), 8.28 (m, 1H), 7.69 (t, 1H), 7.39 (m, 2H), 6.43 (s, 2H)

Workup

  1. temperatureThe reaction mixture was re-cooled to −70° C.
  2. temperatureto warm to room temp over 1 h
  3. stirringwas stirred at room temperature for 2 h
  4. customThe reaction was quenched by the addition of saturated aqueous ammonium chloride
  5. extractionThe reaction mixture was extracted with ethyl acetate
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure to dryness
  9. customThe crude solid product was purified by column chromatography over silica gel

Sources & evidence

ORD record
ord-52ce00ae03f047bba009aa44204df018
Source dataset
uspto-grants-2006_12
Patent number
US07153880B2

Reaction notes

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