Ethylene Glycol → 5-(1,3-Dioxolan-2-YL)-2-fluoropyridine

HRID 1621731

反応式

HRID 1621731 の反応式
[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][N:3]=1.[CH2:10](O)[CH2:11][OH:12].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1.C(=O)(O)[O-].[Na+].O.CCOC(C)=O>[O:7]1[CH2:10][CH2:11][O:12][CH:6]1[C:5]1[CH:8]=[CH:9][C:2]([F:1])=[N:3][CH:4]=1

参加物

8

反応物 3

HCID 174Ethylene GlycolHCID 6101p-Toluenesulfonic acidHCID 164142462-Fluoro-5-formylpyridine

生成物 1

HCID 601557925-(1,3-Dioxolan-2-YL)-2-fluoropyridine収率 64%

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒HCID 516892Sodium Bicarbonate溶媒

反応条件

温度
120 °C

実験手順

6-Fluoronicotinaldehyde (21.96 g, 176 mmol) was suspended in toluene (340 mL) and ethylene glycol (10.4 mL, 186 mmol) and p-toluenesulfonic acid (Acros, 15% in acetic acid, 1.10 mL) were added. The flask was fitted with a Dean-Stark head and a reflux condenser, and placed in a preheated oil bath (120° C.) and the reaction was stirred. After 45 minutes, the reaction was cooled to room temperature. The reaction was diluted with saturated sodium bicarbonate (50 mL), water (150 mL) and EtOAc (150 mL). The layers were separated and the aqueous phase was extracted with EtOAc. The organic phases were combined, dried over sodium sulfate, filtered, concentrated, and purified on a silica gel filter (600 mL fritted filter with about 3 inches of silica gel; DCM to 100:1 to 50:1 DCM/MeOH to 40:1 DCM/MeOH) to give 19.055 g of 5-(1,3-dioxolan-2-yl)-2-fluoropyridine. m/z (ESI, +ve ion) 170 (M+H)+.

後処理

  1. customThe flask was fitted with a Dean-Stark head and a reflux condenser
  2. customplaced in a preheated oil bath
  3. temperaturethe reaction was cooled to room temperature
  4. customThe layers were separated
  5. extractionthe aqueous phase was extracted with EtOAc
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified on a silica gel
  10. filtrationfilter (600 mL fritted filter with about 3 inches of silica gel; DCM to 100:1 to 50:1 DCM/MeOH to 40:1 DCM/MeOH)

出典と根拠

ORDレコード
ord-6fb8bb9bd50d43a9bc974467d858c8e3
出典データセット
uspto-grants-2014_07
特許番号
US08772480B2

関連ノート

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