Cesium fluoride → 7-(2-Fluoro-4-nitrophenoxy)-2-(4-(methylsulfonyl)phenyl)thieno[3,2-b]pyridine

HRID 500770ノート

反応式

HRID 500770 の反応式
Br[C:2]1[S:10][C:9]2[C:4](=[N:5][CH:6]=[CH:7][C:8]=2[O:11][C:12]2[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][C:13]=2[F:21])[CH:3]=1.CC1(C)C(C)(C)OB([C:30]2[CH:35]=[CH:34][C:33]([S:36]([CH3:39])(=[O:38])=[O:37])=[CH:32][CH:31]=2)O1.[F-].[Cs+].C([O-])(O)=O.[Na+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:21][C:13]1[CH:14]=[C:15]([N+:18]([O-:20])=[O:19])[CH:16]=[CH:17][C:12]=1[O:11][C:8]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:3]=[C:2]([C:30]3[CH:35]=[CH:34][C:33]([S:36]([CH3:39])(=[O:38])=[O:37])=[CH:32][CH:31]=3)[S:10][C:9]=12

参加物

8

反応物 4

HCID 25953Cesium fluorideHCID 516892Sodium BicarbonateHCID 27595302-(4-Methanesulfonylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 594245212-Bromo-7-(2-fluoro-4-nitrophenoxy)thieno[3,2-b]pyridine

生成物 1

HCID 587728787-(2-Fluoro-4-nitrophenoxy)-2-(4-(methylsulfonyl)phenyl)thieno[3,2-b]pyridine収率 18%

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

To a solution of 42 (461 mg, 1.3 mmol, scheme 8) in DME (4 mL) was added 4,4,5,5-tetramethyl-2-(4-(methylsulfonyl)phenyl)-1,3,2-dioxaborolane (500 mg, 2.5 mmol), CsF (391 mg, 3.8 mmol), Pd(PPh3)4 (72 mg, 63 μmol) and NaHCO3 (315 mg, 3.8 mmol) pre-dissolved in H2O (1 ml). The reaction mixture was purged with nitrogen and refluxed for 2 hours. The DME was removed under reduced pressure and the aqueous layer was extracted with EtOAc. The extract was dried over sodium sulphate, filtered and evaporated to form a residue which was purified by column chromatography (eluent EtOAc/hexane, 1:1) to afford the title compound 48 (97 mg, 18% yield) as a white solid. 1HNMR (DMSO) δ (ppm): 8.63 (d, J=1.2 Hz, 1H), 8.49 (d-d, J=2.7 Hz, 1H), 8.33 (s, 1H), 8.22-8.19 (m, 2H), 8.16 (s, 2H), 8.02 (d, J=8.6 Hz, 2H), 7.75 (t, J=8.0 Hz, 1H), 7.77-7.58 (m, 2H), 7.58-7.50 (m, 2H), 6.97 (d, J=5.5 Hz, 1H), 3.33 (s, 3H), MS (m/z): 444.8 (M+H).

後処理

  1. customThe reaction mixture was purged with nitrogen
  2. temperaturerefluxed for 2 hours
  3. customThe DME was removed under reduced pressure
  4. extractionthe aqueous layer was extracted with EtOAc
  5. dry with materialThe extract was dried over sodium sulphate
  6. filtrationfiltered
  7. customevaporated
  8. customto form a residue which
  9. customwas purified by column chromatography (eluent EtOAc/hexane, 1:1)

出典と根拠

ORDレコード
ord-6a62fb44ea354771b4ffb5557df5e547
出典データセット
uspto-grants-2010_08
特許番号
US07772247B2

反応ノート

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