Sodium Carbonate → 3-Fluoro[1,1'-biphenyl]-2-amine

HRID 2276730ノート

反応式

HRID 2276730 の反応式
C([O-])([O-])=O.[Na+].[Na+].[C:7]1(B(O)O)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.Br[C:17]1[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[C:18]=1[NH2:19].C([O-])=O.[NH4+]>O.CCOC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC#N.O>[F:24][C:20]1[CH:21]=[CH:22][CH:23]=[C:17]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[C:18]=1[NH2:19]

参加物

9

反応物 4

HCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 2723923Ammonium formateHCID 27829402-Bromo-6-fluoroaniline

生成物 1

HCID 463146263-Fluoro[1,1'-biphenyl]-2-amine

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 18373917Acetonitrile--water (1/1)溶媒

反応条件

温度
50 °C

実験手順

To a solution of Na2CO3 (1.116 g, 10.53 mmol) in water (15 ml) was added poly(ethylene glycol) 2000 (17 g, 5.26 mmol) followed by palladium(II) acetate (0.024 g, 0.105 mmol). The suspension was heated to 50° C. Once the mixture became clear, phenylboronic acid (0.963 g, 7.89 mmol) followed by 2-bromo-6-fluoroaniline (1 g, 5.26 mmol) were added and heated at 120° C. for 30 min. The mixture was cooled, diluted with EtOAc, washed with water, dried and concentrated. The crude material was purified by ISCO (24 g REDISEP® silica column, gradient elution, 0-15% ethyl acetate in hexanes) to give Preparation 5A (800 mg, 81%): LCMS: HPLC: RT=2.016 min (MeCN/H2O with HCOONH4, Ascentis Express C8 2.7 μm 5×2.1 mm, gradient=4 min, wavelength=220 nm); MS(ES): m/z=188 [M+H]+; 1H NMR (CDCl3) δ 7.43-7.48 (m, 4H), 7.35-7.40 (m, 1H), 6.97-7.02 (m, 1H), 6.92 (dt, J=7.6, 1.2 Hz, 1H), 6.71-6.77 (m, 1H), 3.82 (br s, 2H).

後処理

  1. additionwere added
  2. temperatureheated at 120° C. for 30 min
  3. temperatureThe mixture was cooled
  4. washwashed with water
  5. customdried
  6. concentrationconcentrated
  7. customThe crude material was purified by ISCO (24 g REDISEP® silica column, gradient elution, 0-15% ethyl acetate in hexanes)
  8. customto give

出典と根拠

ORDレコード
ord-e8ef268d8c3941569d58a87e702ce06f
出典データセット
uspto-grants-2015_09
特許番号
US09133126B2

反応ノート

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