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

HRID 2276730Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2276730
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]

Komponenten

9

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 18373917Acetonitrile--water (1/1)Lösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-e8ef268d8c3941569d58a87e702ce06f
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09133126B2

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