Sodium Carbonate → 4-(3-Amino-pyrido[2,3-b]pyrazin-6-yl)-2-methoxy-phenol

HRID 1890505

反応式

HRID 1890505 の反応式
Cl[C:2]1[CH:3]=[CH:4][C:5]2[C:6]([N:12]=1)=[N:7][C:8]([NH2:11])=[CH:9][N:10]=2.[CH3:13][O:14][C:15]1[CH:20]=[C:19](B2OC(C)(C)C(C)(C)O2)[CH:18]=[CH:17][C:16]=1[OH:30].C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.O.FC1(F)C(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C1(F)F>[NH2:11][C:8]1[N:7]=[C:6]2[N:12]=[C:2]([C:19]3[CH:18]=[CH:17][C:16]([OH:30])=[C:15]([O:14][CH3:13])[CH:20]=3)[CH:3]=[CH:4][C:5]2=[N:10][CH:9]=1

参加物

7

反応物 3

HCID 10340Sodium CarbonateHCID 27346502-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol2 回HCID 866355376-Chloro-pyrido[2,3-b]pyrazin-3-ylamine

生成物 1

HCID 1361664224-(3-Amino-pyrido[2,3-b]pyrazin-6-yl)-2-methoxy-phenol収率 94.1%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 80711,2-Dimethoxyethane溶媒HCID 9637Perfluoro(methylcyclohexane)溶媒

反応条件

温度
75 °C

実験手順

To a suspension of 1.13 g 6-Chloro-pyrido[2,3-b]pyrazin-3-ylamine (5.94 mmol; 1 eq) and 1.67 g 2-Methoxy-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenol (6.55 mmol; 1.1 eq.) in ethylene glycol dimethyl ether (45 mL) under Ar, a solution of 6.29 g sodium carbonate (59.3 mmol; 10 eq.) in water (20 mL) and a suspension of 378 mg FluoroFlash catalyst (0.24 mmol; 0.04 eq.) in undecafluoro(trifluoromethyl)cyclohexane (45 mL) were added. The mixture was heated to 75° C. for 5 hours. Additional 0.76 g (2.97 mmol; 0.5 eq) of 2-Methoxy-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenol were added and the resulting mixture was stirred at 75° C. for 7.5 hours. After cooling to room temperature, the aqueous and organic phase were separated from the fluorous phase and concentrated in vacuo. The residue was dissolved in methanol and methylene dichloride and filtered. The black solution was again concentrated in vacuo. The residue was taken up in water and the resulting solution was neutralized with 1N HCl whereas the product crystallizes. The brown solid was filtered of, washed with water and dried in vacuo to afford 1.5 g (80.2% yield) of 4-(3-Amino-pyrido[2,3-b]pyrazin-6-yl)-2-methoxy-phenol.

後処理

  1. additionwere added
  2. temperatureAfter cooling to room temperature
  3. customthe aqueous and organic phase were separated from the fluorous phase
  4. concentrationconcentrated in vacuo
  5. dissolutionThe residue was dissolved in methanol
  6. filtrationmethylene dichloride and filtered
  7. concentrationThe black solution was again concentrated in vacuo
  8. customcrystallizes
  9. filtrationThe brown solid was filtered of,
  10. washwashed with water
  11. customdried in vacuo

出典と根拠

ORDレコード
ord-76927f14d6fa41e5ac28a92b3f626229
出典データセット
uspto-grants-2013_08
特許番号
US08507486B2

関連ノート

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