Diethyl Malonate → HCID 67099936、化合物

HRID 2078249ノート

反応式

HRID 2078249 の反応式
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([C:14]([OH:16])=O)[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1.C(Cl)(=O)C(Cl)=O.[C:23]([O:31][CH2:32][CH3:33])(=[O:30])[CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26].[Mg+2].[Cl-].[Cl-]>C(Cl)Cl.CN(C=O)C>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([C:14]([CH:24]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[C:23]([O:31][CH2:32][CH3:33])=[O:30])=[O:16])[CH2:9][CH2:10][O:11][CH2:12][CH2:13]1

参加物

7

反応物 4

HCID 7761Diethyl MalonateHCID 65578Oxalyl chlorideHCID 5360315Magnesium ChlorideHCID 176091224-(2-Fluorophenyl)oxane-4-carboxylic acid

生成物 1

HCID 67099936HCID 67099936、化合物

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

実験手順

To a stirred solution of 4-(2-fluorophenyl)-tetrahydro-2H-pyran-4-carboxylic acid (1.9 g, 8.5 mmol) in DCM (50 mL) and DMF (5 mL) was carefully added oxalyl chloride (0.79 mL, 8.9 mmol). Gas evolution was observed. The reaction was stirred at room temperature for 3 hours. In a separate flask was combined IPAc (1.0 mL, 8.7 mmol), diethyl malonate (1.6 mL, 11 mmol). and anhydrous MgCl2 (1.0 g, 11 mmol). The resulting white slurry was stirred for 30 minutes, and then TEA (4.0 mL, 29 mmol) was added and the reaction was stirred for 2.5 hours. The reaction was chilled in an ice water bath for 10 minutes, and then the concentrated acid chloride oil was added via syringe over 10 minutes. The ice bath was removed, and the reaction was stirred for 16 hours at 50° C. After cooling to room temperature, the reaction was acidified with 5N HCl solution (100 mL). The aqueous layer was removed, and the organic layer was washed with saturated NaHCO3 solution (150 mL). The aqueous layer was removed, and the organic extract was washed with water. The organic layer was dried (Na2SO4), filtered and concentrated to afford a dark colored oil. The crude reaction mixture was used in the next step.

後処理

  1. customIn a separate flask was combined
  2. stirringThe resulting white slurry was stirred for 30 minutes
  3. stirringthe reaction was stirred for 2.5 hours
  4. temperatureThe reaction was chilled in an ice water bath for 10 minutes
  5. customThe ice bath was removed
  6. stirringthe reaction was stirred for 16 hours at 50° C
  7. temperatureAfter cooling to room temperature
  8. customThe aqueous layer was removed
  9. washthe organic layer was washed with saturated NaHCO3 solution (150 mL)
  10. customThe aqueous layer was removed
  11. extractionthe organic extract
  12. washwas washed with water
  13. dry with materialThe organic layer was dried (Na2SO4)
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customto afford a dark colored oil
  17. customThe crude reaction mixture

出典と根拠

ORDレコード
ord-36c0f4dee58945679833523d9f9901a6
出典データセット
uspto-grants-2011_04
特許番号
US07928139B2

反応ノート

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