Dimethylformamide → 5-Cyano-2-(3-methoxy-4-pyridin-2-ylphenyl)-1,3-benzoxazole

HRID 7771

反応式

HRID 7771 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]([C:10]3[CH:15]=[CH:14][C:13]([C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=4)=[C:12]([O:22][CH3:23])[CH:11]=3)=[N:7][C:6]=2[CH:24]=1.[CH3:25][N:26](C=O)C>[C-]#N.[Zn+2].[C-]#N.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:25]([C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]([C:10]3[CH:15]=[CH:14][C:13]([C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=4)=[C:12]([O:22][CH3:23])[CH:11]=3)=[N:7][C:6]=2[CH:24]=1)#[N:26]

参加物

5

反応物 2

HCID 6228DimethylformamideHCID 103093885-Bromo-2-(3-methoxy-4-pyridin-2-ylphenyl)-1,3-benzoxazole

生成物 1

HCID 101498265-Cyano-2-(3-methoxy-4-pyridin-2-ylphenyl)-1,3-benzoxazole

試薬・触媒・溶媒 2

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒

反応条件

温度
120 °C

実験手順

To 1 mL of degassed DMF was added 5-bromo-2-(3-methoxy-4-pyridin-2-ylphenyl)-1,3-benzoxazole (622 mg, 1.63 mmol), zinc cyanide (115 mg, 0.98 mmol), tris(dibenzylideneacetone)-dipalladium (0)-chloroform complex (30 mg, 0.029 mmol), and 1,1′-bisdiphenylphosphinoferrocene (41 mg, 0.073 mmol). The reaction mixture was degassed with argon for an additional 10 min and heated at 120° C. under an argon atmosphere for 20 h. The mixture was cooled to 80° C., 4 mL of a 4:1:4 saturated NH4Cl:NH4OH:H2O solution was added dropwise, and the mixture cooled to rt and stirred overnight. The mixture was cooled to −9° C. and filtered, the solid washed with 5 mL of a 4:1:5 sat. NH4Cl:NH4OH:H2O solution followed by 5 mL H2O, and dried under vacuum to a dark yellow solid. The crude solid was purified by column chromatography (20–80% EtOAc/hexanes) to give 5-cyano-2-(3-methoxy-4-pyridin-2-ylphenyl)-1,3-benzoxazole as a tan solid. 1H NMR (DMSO-d6, 300 MHz) δ 8.72 (d, 1H), 8.47 (d, 1H), 8.09–7.85 (m, 7H), 7.40 (ddd, 1H), 4.01 (s, 3H); MS (ESI) 328 (M+H)+.

後処理

  1. customThe reaction mixture was degassed with argon for an additional 10 min
  2. temperatureThe mixture was cooled to 80° C.
  3. addition4 mL of a 4:1:4 saturated NH4Cl:NH4OH:H2O solution was added dropwise
  4. temperaturethe mixture cooled to rt
  5. temperatureThe mixture was cooled to −9° C.
  6. filtrationfiltered
  7. washthe solid washed with 5 mL of a 4:1:5 sat. NH4Cl
  8. customdried under vacuum to a dark yellow solid
  9. customThe crude solid was purified by column chromatography (20–80% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-dc5c21bbd0c14b558d315caa0f22ae81
出典データセット
uspto-grants-2006_08
特許番号
US07087601B2

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