Triethylamine → (Z)-Ethyl 3-(dimethylamino)-2-(3-fluoropicolinoyl)acrylate

HRID 1497690

反応式

HRID 1497690 の反応式
[CH3:1][N:2]([CH3:10])/[CH:3]=[CH:4]/[C:5]([O:7][CH2:8][CH3:9])=[O:6].C(N(CC)CC)C.[F:18][C:19]1[C:20]([C:25](Cl)=[O:26])=[N:21][CH:22]=[CH:23][CH:24]=1>C1(C)C=CC=CC=1.C(OCC)(=O)C>[CH3:1][N:2]([CH3:10])/[CH:3]=[C:4](/[C:25](=[O:26])[C:20]1[C:19]([F:18])=[CH:24][CH:23]=[CH:22][N:21]=1)\[C:5]([O:7][CH2:8][CH3:9])=[O:6]

参加物

6

反応物 3

HCID 8471TriethylamineHCID 5369162Ethyl trans-3-dimethylaminoacrylateHCID 861023073-Fluoropyridine-2-carbonyl chloride

生成物 1

HCID 86725445(Z)-Ethyl 3-(dimethylamino)-2-(3-fluoropicolinoyl)acrylate収率 16.6%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
83 °C

実験手順

To a light yellow solution of (E)-ethyl 3-(dimethylamino)acrylate (5.15 g, 36.0 mmol) in toluene (50 mL) was added triethylamine (3.64 g, 5.02 mL, 36.0 mmol) at room temperature. To this, a dark brown suspension of 3-fluoropicolinoyl chloride (30) (4.79 g, 30 mmol) in toluene (50 mL, heated to dissolve, but not dissolved completely) was added in one portion using a funnel. Then, the resulting dark brown solution was heated to 83° C. and stirred for 1.5 h at this temperature. During this period, it turned to a dark brown solution and TLC analysis indicated the presence of a new spot. Then, the heating was stopped and the dark brown mixture was diluted with ethyl acetate (200 mL) and the brown solution was washed with water, brine solution, and dried over anhydrous MgSO4. Filtration and concentration gave the crude brown mixture which was purified using ISCO (120 g) column chromatography, eluting with ethyl acetate in hexanes (0 to 100%) and then 5 to 20% methanol in dichloromethane. The desired fractions were combined and the solvent was removed under vacuum to obtain the (Z)-ethyl 3-(dimethylamino)-2-(3-fluoropicolinoyl)acrylate (31) (1.33 g, 15% yield) as a dark brown paste.

後処理

  1. temperatureheated
  2. dissolutionto dissolve
  3. dissolutionnot dissolved completely)
  4. additionwas added in one portion
  5. waitDuring this period
  6. washthe brown solution was washed with water, brine solution
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationFiltration and concentration
  9. customgave the crude brown mixture which
  10. customwas purified
  11. washeluting with ethyl acetate in hexanes (0 to 100%)
  12. customthe solvent was removed under vacuum

出典と根拠

ORDレコード
ord-cf5c752ae14e40ab8d18cc68d78a5194
出典データセット
uspto-grants-2015_12
特許番号
US09199987B2

関連ノート

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