Sodium Carbonate → 4-Fluoro-2-nitro-1,1'-biphenyl

HRID 1776164

Reaktionsgleichung

Reaktionsgleichung von HRID 1776164
Cl[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].CCOCC>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

Komponenten

9

Edukt 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 66827Phenylboronic AcidHCID 676591-Chloro-4-fluoro-2-nitrobenzene

Produkt 1

HCID 113789504-Fluoro-2-nitro-1,1'-biphenylAusbeute 82,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
165 °C

Versuchsvorschrift

A microwave reaction vessel was charged with 2-chloro-5-fluoronitrobenzene (0.175 g, 1 mmol), phenylboronic acid (0.134 g, 1.1 mmol), sodium carbonate (0.317 g, 3 mmol), palladium diacetate (0.009 g, 0.04 mmol), tetrabutylammonium bromide (0.322 g, 1 mmol) in water (2 mL). The mixture was heated to 165° C. in a microwave reactor for 7.5 minutes. The reaction was cooled and poured into ether and 0.1N aqueous sodium hydroxide. The ether layer was washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated. The crude product was purified by silica gel column chromatography (5-30% methylene chloride in hexanes) to give the desired product as a pale yellow oil (0.179 g, 82%). 1H NMR (CDCl3, 300 MHz) δ 7.62-7.58 (dd, 1H, J=2.7, 8.1 Hz), 7.46-7.40 (m, 4H), 7.38-7.34 (m, 1H), 7.31-7.26 (m, 2H). HPLC analysis (C18, 5-95% acetonitrile in H2O+0.1% trifluoroacetic acid over 20 min: retention time, % area at 254 nm): 9.95 min, 96.3%.

Aufarbeitung

  1. customA microwave reaction vessel
  2. temperatureThe reaction was cooled
  3. washThe ether layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel column chromatography (5-30% methylene chloride in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-44c15b57a1cb4f52be96b51a20434241
Quelldatensatz
uspto-grants-2016_02
Patentnummer
US09265772B2

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