Cesium carbonate → 3-Cyclopropyl-2-fluoro-5-nitroaniline

HRID 710214

Reaktionsgleichung

Reaktionsgleichung von HRID 710214
Br[C:2]1[C:3]([F:12])=[C:4]([CH:6]=[C:7]([N+:9]([O-:11])=[O:10])[CH:8]=1)[NH2:5].B1([CH:24]2[CH2:26][CH2:25]2)OC(=O)CN(C)CC(=O)O1.P(C1CCCCC1)(C1CCCCC1)C1CCCCC1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH:24]1([C:2]2[C:3]([F:12])=[C:4]([CH:6]=[C:7]([N+:9]([O-:11])=[O:10])[CH:8]=2)[NH2:5])[CH2:26][CH2:25]1

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 75806TricyclohexylphosphineHCID 441383422-Cyclopropyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dioneHCID 580658073-Bromo-2-fluoro-5-nitroaniline

Produkt 1

HCID 580658083-Cyclopropyl-2-fluoro-5-nitroanilineAusbeute 69,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 22272177Toluene waterLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A mixture of 3-bromo-2-fluoro-5-nitroaniline (2.20 g, 9.36 mmol, 1 equiv), cyclopropylboronic acid MIDA ester (Aldrich; 11.07 g, 56.17 mmol, 6 equiv), Cy3P (1.05 g, 3.74 mmol, 0.4 equiv), Cs2CO3 (54.90 g, 168.50 mmol, 18 equiv) in toluene/H2O (5:1; 450 mL:90 mL) followed by Pd(OAc)2 (0.420 g, 1.87 mmol. 0.20 equiv) was de-gassed by sonicating under vacuum for 10 minutes and back-filled with N2. The mixture was then heated at 100° C. overnight. After allowing to cool to room temperature, the mixture was concentrated to dryness. The residue was taken in DCM, and silica gel was added at this stage so that the residue was absorbed directly on to silica gel. After removing the solvent under vacuum, the crude product was purified by column chromatography on silica gel using DCM to give the product 3-cyclopropyl-2-fluoro-5-nitroaniline (1.27 g, 69%) as a yellow solid.

Aufarbeitung

  1. customwas de-gassed
  2. customby sonicating under vacuum for 10 minutes
  3. additionback-filled with N2
  4. temperatureto cool to room temperature
  5. concentrationthe mixture was concentrated to dryness
  6. additionsilica gel was added at this stage so that the residue
  7. customwas absorbed directly on to silica gel
  8. customAfter removing the solvent under vacuum
  9. customthe crude product was purified by column chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-57f0a91f5ec24e2f81ca8139a28c13a1
Quelldatensatz
uspto-grants-2015_11
Patentnummer
US09181222B2

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