Bromobenzene → 2-Fluoro-5-phenylamino-terephthalic Acid Dimethyl Ester

HRID 970327ノート

反応式

HRID 970327 の反応式
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:13]=[C:12]([F:14])[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[NH2:15].Br[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[CH3:11][O:10][C:8](=[O:9])[C:7]1[CH:6]=[C:5]([NH:15][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:4]([C:3]([O:2][CH3:1])=[O:16])=[CH:13][C:12]=1[F:14]

参加物

7

反応物 3

HCID 7961BromobenzeneHCID 10796Cesium carbonateHCID 16748146Dimethyl 2-amino-5-fluoroterephthalate

生成物 1

HCID 167486382-Fluoro-5-phenylamino-terephthalic Acid Dimethyl Ester収率 80.2%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 634876Binap, (A+-)-触媒HCID 1140Toluene溶媒

反応条件

温度
90 °C

実験手順

To a mixture of 174B (10.0 g, 44.0 mmol), bromobenzene (4.6 mL, 44.0 mmol), (S)-(−)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (2.06 g, 3.30 mmol), and toluene (250 mL) was added cesium carbonate (20.0 g, 44.0 mmol) followed by palladium(II) acetate (0.494 g, 2.20 mmol). The mixture was heated at 90° C. for 24 h. HPLC indicated that the reaction was complete. The reaction mixture was cooled to room temperature, and filtered under reduced pressure through a pad of Celite topped with a pad of silica gel, and the Celite/Silica gel pad was rinsed with EtOAc. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography using a 1:10 mixture of EtOAc and hexane to give 10.7 g (80%) of compound 174C as a pale yellow solid. HPLC retention time=3.72 min. (Condition A). 1H-NMR (400 MHz, CDCl3) δ 3.89 (s, 3H), 3.93 (s, 3H), 7.12 (m, 1H), 7.22 (m, 2H), 7.37 (m, 2H), 7.74 (m, 2H), and 9.22 (br s, 1H).

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered under reduced pressure through a pad of Celite
  3. washthe Celite/Silica gel pad was rinsed with EtOAc
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. custompurified by silica gel chromatography
  6. additiona 1:10 mixture of EtOAc and hexane

出典と根拠

ORDレコード
ord-49b6917dfa0d409ba894878291e297dc
出典データセット
uspto-grants-2007_12
特許番号
US07312209B2

反応ノート

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