Ethanol → Ethyl 5-fluoropyridine-2-carboxylate

HRID 228279

反応式

HRID 228279 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][N:3]=1.C[C:10]([O-:12])=[O:11].[Na+].ClCCl.[CH2:17](O)[CH3:18]>C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Fe]>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:10]([O:12][CH2:17][CH3:18])=[O:11])=[N:3][CH:4]=1

参加物

6

反応物 4

HCID 702EthanolHCID 6344DichloromethaneHCID 517045Sodium AcetateHCID 27831712-Bromo-5-fluoropyridine

生成物 1

HCID 10986675Ethyl 5-fluoropyridine-2-carboxylate収率 68.6%

試薬・触媒・溶媒 1

HCID 178477754HCID 178477754、化合物触媒

反応条件

温度
90 °C

実験手順

To a Parr shaker add 2-bromo-5-fluoropyridine (Example 382, Part A) (7.00 g, 39.8 mmol), NaOAc (13.1 g, 159 mmol), absolute ethanol (100 mL) and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II):dichloromethane (1.62 g, 1.99 mmol). Charge the reaction vessel with 50 psi of CO. Heat at 90° C. for 18.25 hours. Cool the reaction mixture before filtering through a Celite® pad. Wash the pad with ethyl acetate, then concentrate the filtrate. Purify by flash chromatography, eluting with 25% ethyl acetate in hexanes to give the title compound (4.62 g, 68.6%): MS ES+ 169.9 (M+H)+, base peak MS ES+ 141.8 (M+H—CH2CH3)+; HPLC [YMC-Pack Pro C-18 (150×4.6 mm, S-5 microm), 0.1% TFA/acetonitrile in 0.10% TFA/water at 1.0 mL/min, 5-95% over 19 min], tR=10.3 min, 97.0 purity.

後処理

  1. additionCharge the reaction vessel with 50 psi of CO
  2. temperatureCool the reaction mixture
  3. filtrationbefore filtering through a Celite® pad
  4. washWash the pad with ethyl acetate
  5. concentrationconcentrate the filtrate
  6. customPurify by flash chromatography
  7. washeluting with 25% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-02e678da1f434a8bb040b9aea07b74ef
出典データセット
uspto-grants-2009_07
特許番号
US07560463B2

関連ノート

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