Hydrogen Bromide → Ethyl 2-bromo-3-[4-[2-[2-ethyl-4-methyl-6-oxo-1,6-dihydro-1-pyrimidinyl]ethoxy]phenyl]propionate

HRID 382288

反応式

HRID 382288 の反応式
[CH2:1]([C:3]1[N:4]([CH2:11][CH2:12][O:13][C:14]2[CH:20]=[CH:19][C:17](N)=[CH:16][CH:15]=2)[C:5](=[O:10])[CH:6]=[C:7]([CH3:9])[N:8]=1)[CH3:2].[BrH:21].N([O-])=O.[Na+].CN1CCC(=C2C3C(=CC=CC=3)C=CC3C2=CC=CC=3)CC1.[C:48]([O:52][CH2:53][CH3:54])(=[O:51])[CH:49]=[CH2:50]>CC(C)=O.O.[Cu]I>[Br:21][CH:49]([CH2:50][C:17]1[CH:19]=[CH:20][C:14]([O:13][CH2:12][CH2:11][N:4]2[C:5](=[O:10])[CH:6]=[C:7]([CH3:9])[N:8]=[C:3]2[CH2:1][CH3:2])=[CH:15][CH:16]=1)[C:48]([O:52][CH2:53][CH3:54])=[O:51]

参加物

9

反応物 5

HCID 260Hydrogen BromideHCID 2913CyproheptadineHCID 8821Ethyl AcrylateHCID 219601564-[2-[2-Ethyl-4-methyl-6-oxo-1,6-dihydro-1-pyrimidinyl]ethoxy]anilineHCID 23668193Sodium Nitrite

生成物 1

HCID 21960196Ethyl 2-bromo-3-[4-[2-[2-ethyl-4-methyl-6-oxo-1,6-dihydro-1-pyrimidinyl]ethoxy]phenyl]propionate収率 55%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 180Acetone溶媒HCID 962Water溶媒

反応条件

温度
0 °C

実験手順

To a stirred solution of 4-[2-[2-ethyl-4-methyl-6-oxo-1,6-dihydro-1-pyrimidinyl]ethoxy]aniline (2.80 g, 10.26 mmol) (obtained from preparation 22) in acetone (10 ml) was added aqueous HBr (47%, 1 ml) and stirred for 10 min. at 0° C. To the above reaction mixture a solutin of NaNO2 (850 mg, 12.30 mmol) in water (1.7 ml) was added slowly dropwise at 0° C. and stirring was continued further for 30 min at the same temperature. To this reactin mixture, ethyl acrylate (6.77 ml, 62.0 mmol) was added and allowed to warm to 30° C. Catalytic amount of copper (I) iodide (20 mg) was added in one portion and the reaction mixture was stirred further for 1 h at 30° C. Acetone was removed under reduced pressure and the resultant residue was extracted with EtOAc (3×10 ml). The combined EtOAc layers were washed with dilute NH3 solution, water, followed by brine; dried over anhydrous Na2SO4 and concentrated to afford the crude compound which was purified by flash chromatography using 40% EtOAc/petroleum ether as eluent to yield the title compound (2.47 g, 55%).

後処理

  1. stirringstirring
  2. waitwas continued further for 30 min at the same temperature
  3. temperatureto warm to 30° C
  4. stirringthe reaction mixture was stirred further for 1 h at 30° C
  5. customAcetone was removed under reduced pressure
  6. extractionthe resultant residue was extracted with EtOAc (3×10 ml)
  7. washThe combined EtOAc layers were washed with dilute NH3 solution, water
  8. dry with materialdried over anhydrous Na2SO4
  9. concentrationconcentrated
  10. customto afford the crude compound which
  11. customwas purified by flash chromatography

出典と根拠

ORDレコード
ord-7348da8513834e4e96e856472ec2493e
出典データセット
uspto-grants-2001_10
特許番号
US06310069B1

関連ノート

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