Potassium Carbonate → (3-Fluoro-4-formylphenoxy)methyl butyrate

HRID 68248

反応式

HRID 68248 の反応式
[F:1][C:2]1[CH:9]=[C:8]([OH:10])[CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].C([O-])([O-])=O.[K+].[K+].[C:17]([O:22][CH2:23]Cl)(=[O:21])[CH2:18][CH2:19][CH3:20]>CC(C)=O>[C:17]([O:22][CH2:23][O:10][C:8]1[CH:7]=[CH:6][C:3]([CH:4]=[O:5])=[C:2]([F:1])[CH:9]=1)(=[O:21])[CH2:18][CH2:19][CH3:20]

参加物

5

反応物 3

HCID 11430Potassium CarbonateHCID 5872462-Fluoro-4-hydroxybenzaldehydeHCID 2725008Chloromethyl butanoate

生成物 1

HCID 58234674(3-Fluoro-4-formylphenoxy)methyl butyrate収率 66.6%

試薬・触媒・溶媒 1

HCID 180Acetone溶媒3 回

実験手順

To a 500 mL dry round bottom flask a were added 2-fluoro-4-hydroxybenzaldehyde (5.60 g, 40 mmol), anhydrous K2CO3 (10.6 g, 76.9 mmol) and acetone (200 mL). The mixture was stirred at room temperature for 30 minutes. To another 500 mL dry round bottom flash b were added chloromethyl butyrate (9.33 g, 61.5 mmol), KI (14.2 g, 66.6 mmol) and acetone (150 mL). This mixture was also stirred at room temperature for 30 minutes. After the solid settled down on the glassware bottom, the top yellow acetone solution in flask b was decanted into the stirring solution in the round bottom flask a. The resulting mixture was refluxed for 4 hours. Most acetone was rotary evaporated, and the residual solid was triturated with methyl tert-butyl ether (MTBE) three times (100 mL, 50 mL, 50 mL). The MTBE extract was concentrated, and the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give (3-fluoro-4-formylphenoxy)methyl butyrate (6.40 g) as a colorless oil. Yield: 43%. 1H NMR (CDCl3, 300 MHz): δ=10.18 (s, 1H), 7.80 (t, J=8.7 Hz, 1H), 6.93-6.89 (m, 1H), 6.82 (dd, J=12.3, 2.1 Hz, 1H), 5.83 (s, 2H), 2.36 (t, J=7.5 Hz, 2H), 1.64 (sextet, J=7.5 Hz, 2H), 0.92 (t, J=7.5 Hz, 3H). 13C NMR (CDCl3, 75.5 MHz): δ=185.5 (d, J=6.1 Hz), 169.7 (d, J=258.8 Hz), 162.8 (d, J=12.2 Hz), 130.2 (d, J=3.7 Hz), 119.1 (d, J=8.5Hz), 112.4 (d, J=3.1 Hz), 103.5 (d, J=24.4 Hz), 84.1, 35.7, 18.0, 13.3.

後処理

  1. customTo a 500 mL dry round bottom flask
  2. customTo another 500 mL dry round bottom flash b
  3. stirringThis mixture was also stirred at room temperature for 30 minutes
  4. customwas decanted into the stirring solution in the round bottom flask a
  5. temperatureThe resulting mixture was refluxed for 4 hours
  6. customthe residual solid was triturated with methyl tert-butyl ether (MTBE) three times (100 mL, 50 mL, 50 mL)
  7. extractionThe MTBE extract
  8. concentrationwas concentrated
  9. customthe residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

出典と根拠

ORDレコード
ord-e77817fc7c7e4ad1b9d4ad7d1aa59022
出典データセット
uspto-grants-2014_09
特許番号
US08822435B2

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